JP2003012643A - Image-forming material and oligomer used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image-forming material which has excellent image formability and storage stability and does not stain the optimal system of an exposure device, to provide an image-forming material which can form images for direct process using the above image-forming material with IR light laser beams, and to provide a new oligomer capable of being suitably used therefor. SOLUTION: This image-forming material contains a phenol oligomer whose at least one hydroxyl group is modified with an organic group having an IR light-absorbing ability. In detail, the image-forming material contains (a) the phenol oligomer whose at least one hydroxyl group is modified with an organic group having an IR light-absorbing ability and (b) a polymer compound which is soluble in an alkali aqueous solution and whose solubility in the alkali aqueous solution is changed by exposure on IR light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive or negative image-forming material capable of recording an image by exposure to an infrared laser and changing the solubility of the recording layer in the exposed portion, and an oligomer used therein. More specifically, the present invention is writable by exposure in the near infrared region such as an infrared laser, and particularly suitable for a so-called lithographic printing plate precursor for so-called direct plate making which can directly make a plate from a digital signal of a computer, an infrared ray. The present invention relates to an image forming material for a laser and an oligomer which can be suitably used for the same.

[0002]

2. Description of the Related Art In recent years, with the development of solid-state lasers and semiconductor lasers having a light emitting region from near infrared to infrared, as a system for directly making a plate from computer digital data,
The thing using these infrared lasers attracts attention. A positive type lithographic printing plate material for infrared laser for direct plate making is disclosed in JP-A-7-285275. This invention is an image forming material in which a substance that absorbs light and generates heat and a positive photosensitive compound such as a quinonediazide compound are added to an alkali aqueous solution soluble resin, and a positive photosensitive compound is used in the image area. However, it acts as a dissolution inhibitor that substantially reduces the solubility of the alkali aqueous solution soluble resin, and in the non-image area it is decomposed by heat so that it does not develop the dissolution inhibiting ability, and it can be removed by development, and the image is Form.

As a result of the study by the present inventors, it was found that a positive image can be obtained without adding quinonediazide compounds to an image forming material. However, in an image forming material from which quinonediazide compounds are simply removed, There is a drawback that the stability of sensitivity with respect to the concentration of the developing solution, that is, the latitude of development is deteriorated.

On the other hand, it is known that onium salts and alkali-insoluble hydrogen-bondable compounds have an alkali dissolution inhibiting effect on alkali-soluble polymers. WO 97/39894 describes that a composition using a cationic infrared absorbing dye as a dissolution inhibitor of an alkaline water-soluble polymer exhibits a positive action as an infrared laser compatible image forming material. This positive action is a function in which the infrared absorbing dye absorbs the laser light and the generated heat eliminates the dissolution inhibiting effect of the polymer film in the irradiated portion to form an image. Although the image forming material by such infrared laser exposure can exhibit sufficient image forming property on the laser-irradiated surface,
Due to heat diffusion, it is difficult to obtain a sufficient effect to the deep part of the sensitive material,
There were problems such as low sensitivity and narrow development latitude. The development latitude referred to here means an allowable range in which good image formation can be performed when the alkali concentration of the alkali developer is changed.

In order to solve the problem of low sensitivity to exposure, for example, a so-called chemical amplification type light-sensitive material as disclosed in Japanese Patent Laid-Open No. 11-65105, and Japanese Patent Laid-Open No. 200-200.
A photosensitive material utilizing polymerization of an ethylenically unsaturated compound as disclosed in JP-A-0-89455 has been studied,
Since such a light-sensitive material contains a component excellent in reactivity to light and heat, an undesired reaction is likely to occur due to handling under white light or storage or a change in environmental temperature, and there is a concern that storage stability is poor. There is. In addition, if the exposure amount is increased to obtain sufficient image forming property and development latitude,
There is also a problem that ablation of the infrared absorber and other components in the photosensitive layer occurs, and the optical system of the exposure machine is contaminated.

For the purpose of easily achieving film strength (image strength) when used as an image forming material, for example, US Pat.
No. 124425 describes an example of an alkali-soluble resin having an infrared absorbing functional group in its side chain. That is, it is intended to improve the film strength by introducing a partial structure having a photothermal conversion function into the alkali-soluble resin to reduce the components in the material. However, since this alkali-soluble resin is a high molecular weight compound having a molecular weight of 5,000 or more, its adhesion to the base material becomes great and its solubility in the processing agent at the time of development becomes insufficient. When used as a mold-type image forming material, the solubility of the non-image area is low, the recording layer to be removed is not sufficiently removed by the development process, and a residual film easily stains on the non-image area. Had a problem.

[0007]

Therefore, an object of the present invention is to provide an image forming material which is excellent in image forming property and storage stability and does not contaminate the optical system of an exposure apparatus, and an infrared laser for direct plate making using the same. An object of the present invention is to provide an image forming material capable of forming an image and a novel oligomer which can be suitably used for the image forming material.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies for the purpose of improving the image-forming property and the storage stability, and as a result, have found that an image-forming material in which a group having an infrared absorbing ability is introduced into a specific oligomer is introduced. It was found that the use thereof improves both the image forming property and the storage stability, and the ablation of the infrared absorbent can be suppressed, and the present invention has been completed.

That is, the image-forming material of the present invention is characterized in that an image can be recorded by exposure to infrared rays, and at least one hydroxyl group contains a phenol oligomer modified with an organic group having an infrared absorption ability. More specifically, the image-forming material of the present invention is a heat-mode-compatible image-forming material, wherein (a) at least one hydroxyl group is modified with an organic group having infrared absorption ability, and (b) an alkali. A positive or negative image-forming material containing a polymer compound soluble in an aqueous solution, the solubility of which changes in an aqueous alkali solution upon exposure to infrared light, or (a) an organic material having at least one hydroxyl group capable of absorbing infrared rays. It is an image-forming material containing a phenol oligomer modified with a group, the hydrophilicity and hydrophobicity of the surface of which is changed by infrared exposure.

Further, the phenol oligomer of the present invention according to claim 3 is characterized in that at least one hydroxyl group is modified with an organic group having an infrared absorbing ability.

Although the function of the present invention is not clear, the phenol oligomer used in the image-forming material of the present invention is modified with an organic group having an infrared-absorbing ability so that it functions as an infrared-absorbing agent and an image-forming component. With the original properties of the polymer having a phenol skeleton, which is useful as such, the heat generated in the organic group having a photothermal conversion function directly acts on the phenol oligomer, and the improvement of the image forming property can be achieved. Conceivable.

Further, since an organic group having an infrared absorbing ability is bonded to the oligomer, precipitation from the photosensitive layer due to crystallization of the photothermal conversion material when the photosensitive material is stored for a long period of time or the photothermal conversion material and the binder are carried out. It is considered that the storage stability is improved because the strength of the interaction with other components in the photosensitive layer such as does not easily change. Furthermore, since the organic group having infrared absorption ability is bonded to the oligomer that is difficult to scatter by ablation, it is considered that the scattering of the organic compound having infrared absorption ability due to heat generation during exposure due to ablation can be suppressed. Further, since the phenol oligomer of the present invention has a phenolic hydroxyl group, the solubility in an alkali developing solution is improved, and since the molecular weight is appropriately small, adsorption on the surface of the support is less likely to occur. The stain resistance of the image area can be improved.

In the present invention, "heat mode compatible" means that recording by heat mode exposure is possible. Hereinafter, the definition of heat mode exposure in the present invention will be described in detail. Hans-Joachim
Time, IS & Ts NIP 15: 1999 I
international Conference o
n Digital Printing Technology
logs. P. 209, photoexcitation of a light-absorbing substance (for example, a dye) in a photosensitive material, which undergoes a chemical or physical change, resulting in a chemical or physical change from the photoexcitation of the light-absorbing substance forming an image. It is known that there are two modes in the process up to. One is that the photoexcited light-absorbing substance is deactivated by some photochemical interaction (for example, energy transfer or electron transfer) with other reactants in the photosensitive material, and as a result, the activated reactant is The so-called photon mode that causes the above-mentioned chemical or physical changes necessary for image formation is the second, in which the photoexcited light-absorbing substance generates heat and is deactivated, and the heat is used to cause the reaction substance to react. This is a so-called heat mode that causes a chemical or physical change necessary for image formation. There are also special modes such as ablation in which substances explode explosively due to the energy of light locally collected, and multiphoton absorption in which one molecule absorbs many photons at a time, but they are omitted here.

The exposure process utilizing each of the above modes is called photon mode exposure and heat mode exposure. The technical difference between photon mode exposure and heat mode exposure is whether or not the energy amount of several photons to be exposed can be added to the energy amount of the desired reaction.
For example, consider using n photons to cause a certain reaction. Since photon mode exposure utilizes photochemical interaction, one photon energy cannot be added together due to the requirement of quantum energy and momentum conservation law. That is, in order to cause some kind of reaction, the relationship of “one-photon energy amount ≧ reaction energy amount” is necessary. On the other hand, in heat mode exposure, heat is generated after photoexcitation, and light energy is converted into heat and used, so that the energy amounts can be added together. Therefore, the relationship of “energy amount of n photons ≧ energy amount of reaction” is sufficient. However, the addition of this energy amount is restricted by thermal diffusion. That is, if the next photoexcitation-deactivation process occurs and heat is generated before the heat escapes from the exposed portion (reaction point) that is currently being noticed by heat diffusion, the heat is surely accumulated and added, and the temperature of that portion rises. Leads to. However, when the next generation of heat is slow, the heat escapes and is not accumulated. In other words, in heat mode exposure, even if the total exposure energy amount is the same, the results are different when high-energy light is irradiated for a short time and when low-energy light is irradiated for a long time. Will be advantageous to the accumulation of.

Of course, in photon mode exposure, a similar phenomenon may occur due to the influence of diffusion of the subsequent reaction species, but basically, such a phenomenon does not occur. In other words, in terms of the characteristics of the photosensitive material, in the photon mode, the intrinsic sensitivity of the photosensitive material (energy for reaction necessary for image formation) with respect to the exposure power density (W / cm ² ) (= energy density per unit time) However, in the heat mode, the intrinsic sensitivity of the photosensitive material increases with the exposure power density. Therefore, when the exposure time is fixed so that the productivity required for practical use as an image forming material is fixed, the photon mode exposure usually has a high sensitivity of about 0.1 mJ / cm ² when comparing each mode. Can be achieved, but the reaction takes place at any low light exposure,
The problem of low-exposure fog in the unexposed area is likely to occur. On the other hand, in the heat mode exposure, the reaction does not occur unless the exposure amount is a certain amount or more, and about 50 mJ / cm ² is usually required in relation to the thermal stability of the photosensitive material, but the problem of low exposure fog occurs. Is avoided.

In fact, in heat mode exposure, the exposure power density on the plate surface of the photosensitive material needs to be 5000 W / cm ² or more, preferably 10,000 W / cm ² or more. However, although not described here in detail, it is not preferable to use a high power density laser of 5.0 × 10 ⁵ W / cm ² or more because ablation occurs and the light source is contaminated.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The image forming material of the present invention is characterized in that at least one hydroxyl group contains a phenol oligomer modified with an organic group having an infrared absorbing ability, and recording by infrared exposure is possible. More specifically, the image forming material of the present invention includes (a) a phenol oligomer in which at least one hydroxyl group is modified with an organic group having an infrared absorbing ability,
And (b) a polymer compound soluble in an alkaline aqueous solution is contained, and the solubility in the alkaline aqueous solution is changed by infrared exposure. Hereinafter, the image forming material of the present invention and the novel phenol oligomer used therein will be described in detail.

[(A) Phenol Oligomer Having at least One Hydroxyl Group Modified with an Organic Group Having Infrared Absorption] The phenol oligomer having at least one hydroxyl group modified with an organic group having infrared absorption (hereinafter , Is appropriately referred to as an infrared absorbing oligomer.) Can be obtained by hydrogen bonding a compound having infrared absorbing ability to at least one of the phenolic hydroxyl groups in the phenol oligomer by various bonding modes. It has been found that an oligomer having such a structure is a novel compound and is useful as an image forming material. The infrared absorbing oligomer of the present invention preferably has two or more phenol skeletons, and if at least one phenolic hydroxyl group remains unmodified in the molecule, the solubility in an alkaline developer is improved. It is preferable from the viewpoint of improving the stain resistance of the non-image area. Further, the phenol skeleton of the infrared absorbing oligomer of the present invention has 2
It is preferably 0 or less, and more preferably 10 or less. Hereinafter, (1) a phenol oligomer and (2) a compound having an infrared absorbing ability, which are constituent components of the infrared absorbing oligomer of the present invention, will be described.

(1) Phenol Oligomer Examples of the phenol oligomer that can be used in the infrared absorbing oligomer of the present invention include 2,3,4-trihydroxybenzophenone, 2,4,4'-trihydroxybenzophenone and 2,4. , 6-trihydroxybenzophenone, 2,3,4-trihydroxy-2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2 , 4,6,3 ', 4'-pentahydroxybenzophenone, 2,3,4,2', 4'-pentahydroxybenzophenone, 2,3,4,2 ',
5'-pentahydroxybenzophenone, 2,4,6
3 ', 4', 5'-hexahydroxybenzophenone,
Polyhydroxybenzophenones such as 2,3,4,3 ′, 4 ′, 5′-hexahydroxybenzophenone,

Polyhydroxyphenyl alkyl ketones such as 2,3,4-trihydroxyacetophenone, 2,3,4-trihydroxyphenyl pentyl ketone and 2,3,4-trihydroxyphenylhexyl ketone, bis (2,4) -Dihydroxyphenyl) methane, bis (2,2
3,4-trihydroxyphenyl) methane, bis (2,2
4-dihydroxyphenyl) propane-1, bis (2,2
3,4-trihydroxyphenyl) propane-1, bis ((poly) hydroxyphenyl) alkanes such as nordihydroguaiaretic acid,

Propyl 3,4,5-trihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate,
Polyhydroxybenzoic acid esters such as phenyl 3,4,5-trihydroxybenzoate, bis (2,3,4-trihydroxybenzoyl) methane, bis (3-acetyl-4,5,6-trihydroxyphenyl) -Bis (polyhydroxybenzoyl) alkane or bis (polyhydroxybenzoyl) aryls such as methane, bis (2,3,4-trihydroxybenzoyl) benzene, bis (2,4,6-trihydroxybenzoyl) benzene,

Ethylene glycol-di (3,5-dihydroxybenzoate), ethylene glycol-di (3,3
4,5-trihydroxybenzoate) and other alkylene-di (polyhydroxybenzoates), 2,3,4-
Biphenyltriol, 3,4,5-biphenyltriol, 3,5,3 ', 5'-biphenyltetrol,
2,4,2 ', 4'-biphenyl tetrol, 2,4
6,3 ', 5'-biphenylpentol, 2,4,6
2 ', 4', 6'-biphenylhexol, 2,3
Polyhydroxybiphenyls such as 4,2 ′, 3 ′, 4′-biphenylhexol,

Bis (polyhydroxy sulfides) such as 4,4'-thiobis (1,3-dihydroxy) benzene,
Bis (polyhydroxyphenyl) ethers such as 2,2 ′, 4,4′-tetrahydroxydiphenyl ether,
Bis (polyhydroxyphenyl) sulfoxides such as 2,2 ′, 4,4′-tetrahydroxydiphenyl sulfoxide, bis (polyhydroxyphenyl) sulfones such as 2,2 ′, 4,4′-diphenyl sulfone,

Tris (4-hydroxyphenyl) methane, 4,4 ', 4''-trihydroxy-3,5
3 ', 5'-tetramethyltriphenylmethane, 4,
4 ', 3 ", 4" -tetrahydroxy-3,5
3 ', 5'-tetramethyltriphenylmethane, 4,
4 ', 2 ", 3", 4 "-pentahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane, 2,3,4,2', 3 ', 4'-hexahydroxy-5,5'-diacetyltriphenylmethane, 2,3,3
4,2 ', 3', 4 ', 3 ", 4"-octahydroxy-5,5'-diacetyltriphenylmethane, 2,
4,6,2 ', 4', 6'-hexahydroxy-5,5
Polyhydroxytriphenylmethanes such as 5′-dipropionyltriphenylmethane,

3,3,3 ', 3'-tetramethyl-1,
1'-spirobi-indane-5,6,5 ', 6'-tetrol, 3,3,3', 3'-tetramethyl-1,1 '
-Spirobi-indan-5,6,7,5 ', 6', 7 '
-Hexool, 3,3,3 ', 3'-tetramethyl-
1,1'-spirobi-indane-4,5,6,4 ',
5 ', 6'-hexool, 3,3,3', 3'-tetramethyl-1,1'-spirobi-indane-4,5,5
Polyhydroxyspirobi-indanes such as 6,5 ′, 6 ′, 7′-hexool,

3,3-bis (3,4-dihydroxyphenyl) phthalide, 3,3-bis (2,3,4-trihydroxyphenyl) phthalide, 3 ', 4', 5 ', 6'-
Polyhydroxyphthalides such as tetrahydroxyspiro [phthalide-3,9′-xanthene], flavono dyes such as morin, quercetin and rutin,

Α, α ', α''-tris (4-hydroxyphenyl) 1,3,5-triisopropylbenzene,
α, α ′, α ″ -tris (3,5-dimethyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,5-diethyl-
4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,5-di-n)
-Propyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (3,5-diisopropyl-4-hydroxyphenyl)
1,3,5-triisopropylbenzene, α, α ′,
α ″ -tris (3,5-di-n-butyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene,
α, α ′, α ″ -tris (3-methyl-4-hydroxyphenyl) 1,3,5-triisopropylbenzene,
α, α ′, α ″ -tris (3-methoxy-4-hydroxyphenyl) 1,3,5-triisopropylbenzene, α, α ′, α ″ -tris (2,4-dihydroxyphenyl) 1, 3,5-triisopropylbenzene,
1,3,5-Tris (3,5-dimethyl-4-hydroxyphenyl) benzene, 1,3,5-tris (5-methyl-2-hydroxyphenyl) benzene, 2,4,6-
Tris (3,5-dimethyl-4-hydroxyphenylthiomethyl) mesitylene, 1- [α-methyl-α- (4 ′
-Hydroxyphenyl) ethyl] -4- [α, α'-bis (4 ''-hydroxyphenyl) ethyl] benzene,
1- [α-methyl-α- (4′-hydroxyphenyl)
Ethyl] -3- [α, α′-bis (4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α-
(3 ', 5'-dimethyl-4'-hydroxyphenyl)
Ethyl] -4- [α, α′-bis (3 ″, 5 ″ -dimethyl-4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (3′-methyl-4) '-Hydroxyphenyl) ethyl] -4- [α', α'-bis (3 ''-methyl-4 ''-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (3'-methoxy) -4'-Hydroxyphenyl) ethyl] -4-
[Α ′, α′-bis (3 ″ -methoxy-4 ″ -hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α- (2 ′, 4′-dihydroxyphenyl) ethyl]
-4- [α ', α'-bis (4''-hydroxyphenyl) ethyl] benzene, 1- [α-methyl-α-
(2 ', 4'-Dihydroxyphenyl) ethyl] -3-
[Α ″, α′-bis (4 ″ -hydroxyphenyl)
Ethyl] benzene, etc., the polyhydroxy compound described in JP-A-4-253058,

P-bis (2,3,4-trihydroxybenzoyl) benzene, p-bis (2,4,6-trihydroxybenzoyl) benzene, m-bis (2,3,4-)
Trihydroxybenzoyl) benzene, m-bis (2,2
4,6-trihydroxybenzoyl) benzene, p-bis (2,5-dihydroxy-3-bromobenzoyl) benzene, p-bis (2,3,4-trihydroxy-5-)
Methylbenzoyl) benzene, p-bis (2,3,4-
Trihydroxy-5-methoxybenzoyl) benzene,
p-bis (2,3,4-trihydroxy-5-nitrobenzoyl) benzene, p-bis (2,3,4-trihydroxy-5-cyanobenzoyl) benzene, 1,3,5
-Tris (2,5-dihydroxybenzoyl) benzene, 1,3,5-tris (2,3,4-trihydroxybenzoyl) benzene, 1,2,3-tris (2,3,3)
4-trihydroxybenzoyl) benzene, 1,2,4
-Tris (2,3,4-trihydroxybenzoyl) benzene, 1,2,4,5-tetrakis (2,3,4-trihydroxybenzoyl) benzene, α, α'-bis (2,3,4-) Trihydroxybenzoyl) -p-xylene, α, α ′, α′-tris (2,3,4-trihydroxybenzoyl) mesitylene,

2,6-bis- (2'-hydroxy-
3 ', 5'-dimethyl-benzyl) -p-cresol,
2,6-bis- (2'-hydroxy-5'-methyl-benzyl) -p-cresol, 2,6-bis- (2'-hydroxy-3 ', 5'-di-t-butyl-benzyl) −
p-cresol, 2,6-bis- (2'-hydroxy-
5'-ethyl-benzyl) -p-cresol, 2,6-
Bis- (2 ', 4'-dihydroxy-benzyl) -p-
Cresol, 2,6-bis- (2'-hydroxy-3 '
-T-butyl-5'-methyl-benzyl) -p-cresol, 2,6-bis- (2 ', 3', 4'-trihydroxy-5'-acetyl-benzyl) -p-cresol,
2,6-bis- (2 ', 4', 6'-trihydroxy-
Benzyl) -p-cresol, 2,6-bis- (2 ',
3 ', 4'-trihydroxy-benzyl) -p-cresol, 2,6-bis- (2', 3 ', 4'-trihydroxy-benzyl) -3,5-dimethyl-phenol,
4,6-bis- (4'-hydroxy-3 ', 5'-dimethyl-benzyl) -pyrogallol, 4,6-bis-
(4'-Hydroxy-3 ', 5'-dimethoxy-benzyl) -pyrogallol, 2,6-bis- (4'-hydroxy-3', 5'-dimethyl-benzyl) -1,3,4-
Trihydroxy-phenol, 4,6-bis- (2 ',
4 ', 6'-trihydroxy-benzyl) -2,4-dimethyl-phenol, 4,6-bis- (2', 3 ',
4'-trihydroxy-benzyl) -2,5-dimethyl-phenol and the like can be mentioned.

The polyhydroxy compounds [I-1] to [IV-2] described in JP-A-8-190194,
Water-insoluble alkali-soluble low-molecular compound (01) having an aromatic hydroxyl group described in JP-A-8-272091
(102), and the polyhydroxy compounds [V-1] to [VII-12] described in JP-A-8-254824 can also be preferably used. Further, low cores of novolac resins, phenol resins such as polyhydroxystyrene, etc. The body can also be used. In that case, the molecular weight of the low nucleus is 3,000.
The following is preferable, and 2,000 or less is more preferable. These oligomers may be used alone or in combination of two or more.

Further, among these oligomers, from the viewpoints of availability, solubility and image forming property after modification with an organic group having an infrared absorbing ability, the following general formulas (1) and (2) are used. An oligomer having a partial structure is particularly preferable.

[0032]

[Chemical 1]

In the above general formulas (1) and (2), m and n each independently represent an integer of 0 to 3, and the sum of m and n is 2 or more. k represents an integer of 1 to 3, and A represents any organic group.

These phenol oligomers are (2) a phenol oligomer modified by an organic group having infrared absorption ability by being covalently bonded to a compound having infrared absorption ability described later, that is, as an infrared absorption oligomer. used.

(2) Compound Having Infrared Absorption The compound having infrared absorption has an infrared absorption having a functional group capable of forming a bond with the above-mentioned phenol oligomer and absorbing infrared light to generate heat. There is no particular limitation as long as it is a compound having The infrared absorbing compound used here is not particularly limited as long as it is a chromophore that has absorption in the infrared region.

That is, when the compound having an infrared absorbing ability of the present invention is used as an image forming material, it is heated by infrared exposure like an infrared absorbing agent contained in a general recording material capable of forming an image by exposure in the infrared region. It has a function of performing an image formation by the heat. Therefore, the infrared absorbent oligomer of the present invention is required to have a dye group capable of absorbing infrared rays that efficiently converts the light of the infrared laser into heat. The chromophore having an infrared absorbing ability used here has absorption in the near infrared region, but specifically has absorption in the wavelength range of 720 nm to 1200 nm,
Preferably, it has an absorption maximum at a wavelength of 720 nm to 1200 nm.

The compound having infrared absorbing ability is a polymethine dye such as a cyanine dye, a (thio) pyrylium dye, an oxonol dye, or a phthalocyanine dye from the viewpoint of image forming property and solvent solubility when used as an image forming material. Organic dyes are preferred, and particularly preferred polymethine dyes include dyes having the structure of the following general formula (I).

[0038]

[Chemical 2]

In the above general formula (I), R ¹ and R ² each independently represent an alkyl group having 1 to 12 carbon atoms, and an alkoxy group, an aryl group, an amido group, an alkoxycarbonyl group, It may have a substituent selected from a hydroxyl group, a sulfo group and a carboxyl group. Y ¹ and Y ² are each independently oxygen, sulfur, selenium, a dialkylmethylene group or-
Represents CH = CH-. Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group or a heterocyclic group, and are an alkyl group, an alkoxy group, a halogen atom, an alkoxycarbonyl group, an alkyl (oxy) sulfonyl group, an aryl (oxy) sulfonyl group, a halogen-substituted group. A hydrocarbon group having a naphthalene skeleton is preferable, which may have a substituent selected from an alkyl group, and an aromatic ring may be condensed with two consecutive carbon atoms adjacent to Y ¹ and Y ² .

X represents a counter ion required for charge neutralization, and is not always necessary when the dye cation portion has an anionic substituent. Q represents a trimethine group, a pentamethine group, a heptamethine group, a nonamethine group or an undecamethine group, which is preferably substituted with a chlorine atom on any of the carbon atoms, and a cyclohexene ring or cyclopentene ring containing three consecutive methine chains. Having a ring is preferable from the viewpoint of stability.

By binding such a polymethine dye to (1) a phenol oligomer, an infrared absorbing oligomer having absorption of the bound polymethine dye can be obtained. As the polymethine dye, the maximum absorption wavelength is 750. It is preferable to use those having a thickness of up to 1200 nm.

The above-mentioned (1) phenol oligomer and (2) compound having infrared absorbing ability are covalently bonded by various bonding modes, such as ether bond and (thio) urethane bond. , Ester bond,
Bonds such as a (thio) thiourea bond and an amide bond are preferred, and an ether bond and a (thio) urethane bond are particularly preferred from the viewpoint of ease of synthesis and availability of raw materials.

The above (1) phenol oligomer,
(2) Specific examples of the phenol oligomer synthesized with the compound having infrared absorption ability and having at least one hydroxyl group modified with the organic group having infrared absorption ability will be illustrated below, but the present invention is not limited to these. Not something. In addition, in the following formula, at least one of R ^{1 to} R ³ represents an organic group having the following infrared absorbing ability, and at least one represents a hydrogen atom.

[0044]

[Chemical 3]

[0045]

[Chemical 4]

[0046]

[Chemical 5]

[0047]

[Chemical 6]

The infrared absorbing oligomer of the present invention has a weight average molecular weight of preferably 500 or more, more preferably 750 to 5,000.
Further, the number average molecular weight thereof is preferably 500 or more, more preferably 600 to 4,500.
Polydispersity (weight average molecular weight / number average molecular weight) is 1.0 to 1
It is preferably 0.

In the infrared absorbing oligomer of the present invention, the constitutional ratio of constitutional units derived from (1) phenol oligomer and (2) compound having infrared absorbing ability is preferably 1: 1 to 1: 6. , 1: 1 to 1: 4 are more preferable. Here, when the constitutional unit derived from the compound having infrared absorbing ability is less than 1 with respect to the constitutional unit 1 derived from phenol oligomer, the ratio of the phenol oligomer not having infrared absorbing ability becomes large, so that the image forming property becomes poor. descend. On the other hand, when the number of the structural units derived from the compound having the infrared absorbing ability is more than 6 with respect to the structural unit 1 derived from the phenol oligomer, there arises a problem that the solvent solubility is lowered and the synthesis becomes difficult.

When the infrared absorbing oligomer is contained in the image forming material of the present invention, only one kind may be added, or two or more kinds may be mixed and used. In the present invention, the content of these infrared absorbing oligomers depends on the introduction rate of the structural unit derived from the compound having infrared absorbing ability bonded to the phenol skeleton in the phenol oligomer. The content is 0.01 to 50% by weight based on the total solid content of the image forming material,
Preferably 0.1 to 20% by weight, more preferably 0.5.
When the content is less than 0.01% by weight, the image formability is deteriorated, and when the content exceeds 50% by weight, the film formability and the non-formability are deteriorated when used as a recording layer of a lithographic printing plate precursor. The removability of the image part may deteriorate.

As the other components contained in the image forming material of the present invention, various known components of image forming materials capable of recording with infrared rays can be appropriately selected and used. First,
An image forming material whose solubility in an alkaline aqueous solution changes by infrared exposure will be described. Such image-forming materials are classified into a positive type in which solubility in an alkaline aqueous solution is improved and a negative type in which the solubility in an alkaline aqueous solution is decreased by exposure to infrared rays.

Examples of the positive type image forming material include interaction releasing type (heat-sensitive positive type) and acid catalyst decomposing type image forming materials. These are soluble in water or alkaline water due to the action of releasing the bond of the polymer compound forming the layer by the acid generated by light irradiation or heating or the thermal energy itself, and are removed by development to be non-soluble. The image portion is formed.

Examples of the negative type image forming material include radical polymerization type and acid catalyst cross-linking type (including cationic polymerization) image forming materials. In these, radicals or acids generated by light irradiation or heating serve as initiators or catalysts,
The compound constituting the image forming material undergoes a polymerization reaction and a crosslinking reaction to be cured to form an image portion. Hereinafter, each of the positive type and negative type image forming materials will be described in detail.

<Interaction-releasing system (heat-sensitive positive)> The interaction-releasing system image-forming material is composed of (b) a polymer compound soluble in an alkaline aqueous solution and (a) an infrared absorbing oligomer described above. To be done.

[(B) Polymer Compound Soluble in Alkaline Aqueous Solution] (b) Polymer compound soluble in an alkaline aqueous solution (hereinafter
Appropriately referred to as an alkali-soluble resin) includes a homopolymer having an acidic group in the main chain and / or side chain in a polymer, a copolymer thereof, or a mixture thereof.
Among them, those having an acidic group described in the following (1) to (6) in the main chain and / or side chain of the polymer are preferable from the viewpoint of solubility in an alkaline developing solution and manifestation of dissolution inhibiting ability.

[0056] (1) phenol group (-Ar-OH) (2) sulfonamide group _{(-SO 2 NH-R) (} 3) substituted sulfonamide-based acid group [(hereinafter, referred to as "active imide group".) - _{SO 2 NHCOR, -SO 2 NHSO 2} R, -CON
HSO ₂ R] (4) carboxylic acid group (-CO ₂ H) (5) sulfonic acid group (-SO ₃ H) (6) phosphoric acid group (-OPO ₃ H ₂₎

In the above (1) to (6), Ar represents a divalent aryl linking group which may have a substituent, and R represents a hydrocarbon group which may have a substituent. .

Among the alkali-soluble resins having an acidic group selected from the above (1) to (6), the alkali-soluble resin having (1) phenol group, (2) sulfonamide group and (3) active imide group is preferable. In particular, an alkali-soluble resin having (1) a phenol group or (2) a sulfonamide group is most preferable from the viewpoint of ensuring sufficient solubility in an alkaline developing solution, development latitude and film strength.

Examples of the alkali-soluble resin having an acidic group selected from the above (1) to (6) include the following. (1) Examples of the alkali-soluble resin having a phenol group include a condensation polymer of phenol and formaldehyde, a condensation polymer of m-cresol and formaldehyde,
Condensation polymer of p-cresol and formaldehyde, m-
/ P-condensation polymer of mixed cresol and formaldehyde, phenol and cresol (m-, p-, or m- /
and a novolak resin such as a condensation polymer of formaldehyde, and a condensation polymer of pyrogallol and acetone. Further, a copolymer obtained by copolymerizing a compound having a phenol group in its side chain can be mentioned. Alternatively, a copolymer obtained by copolymerizing a compound having a phenol group on its side chain can be used.

Examples of the compound having a phenol group include acrylamide, methacrylamide, acrylic acid ester, methacrylic acid ester, and hydroxystyrene having a phenol group.

As the alkali-soluble resin (2) having a sulfonamide group, for example, a polymer having a minimum constitutional unit derived from a compound having a sulfonamide group as a main constituent can be mentioned. Examples of the compound as described above include a compound having at least one sulfonamide group in which at least one hydrogen atom is bonded to a nitrogen atom and a polymerizable unsaturated group in the molecule. Among them, a low molecular weight compound having an acryloyl group, an allyl group, or a vinyloxy group, and a substituted or mono-substituted aminosulfonyl group or a substituted sulfonylimino group in the molecule is preferable, for example, represented by the following general formula 1 to general formula 5. The compound to be mentioned is mentioned.

[0062]

[Chemical 7]

[Where X is¹, X²Are independently -O
-Or NR²⁷Represents-. R^{twenty one}, R^{twenty four}Each independently
Hydrogen atom or CH₃Represents R^{twenty two}, R^{twenty five}, R²⁹, R³²Over
And R³⁶Are carbons each optionally having a substituent.
An alkylene group having a prime number of 1 to 12, a cycloalkylene group,
It represents a rylene group or an aralkylene group. R^{twenty three}, R²⁷as well as
R³³Each independently have a hydrogen atom and a substituent.
Good alkyl group having 1 to 12 carbon atoms, cycloalkyl
Represents a group, an aryl group or an aralkyl group. Also, R ²⁶,
R³⁷Each independently represents a carbon that may have a substituent.
Number 1 to 12 alkyl group, cycloalkyl group, aryl
Group represents an aralkyl group. R²⁸, R³⁰And R ³⁴Is it
Independently hydrogen atom or CH₃Represents R³¹, R³⁵Is
Each may independently have a single bond or a substituent.
An alkylene group having 1 to 12 carbon atoms, a cycloalkylene group,
It represents an arylene group or an aralkylene group. Y³, Y^FourIs
Each independently represents a single bond or CO-. ]

Among the compounds represented by the general formulas 1 to 5, in the positive type lithographic printing material of the present invention, particularly m-aminosulfonylphenyl methacrylate, N- (p-aminosulfonylphenyl) methacrylamide, N- (P-Aminosulfonylphenyl) acrylamide and the like can be preferably used.

As the alkali-soluble resin having an active imide group (3), for example, a polymer having a minimum constitutional unit derived from a compound having an active imide group as a main constitutional component can be mentioned. Examples of the compound as described above include compounds having one or more active imide groups represented by the following structural formulas and at least one polymerizable unsaturated group in the molecule.

[0066]

[Chemical 8]

Specifically, N- (p-toluenesulfonyl) methacrylamide, N- (p-toluenesulfonyl) acrylamide and the like can be preferably used.

(4) As the alkali-soluble resin having a carboxylic acid group, for example, a main constituent is a minimum structural unit derived from a compound having at least one carboxylic acid group and at least one polymerizable unsaturated group in the molecule. The polymer used as a component can be mentioned. (5) As the alkali-soluble polymer having a sulfonic acid group, for example, a minimum structural unit derived from a compound having at least one sulfonic acid group and at least one polymerizable unsaturated group in the molecule is a main structural unit. Polymers can be mentioned. (6) As the alkali-soluble resin having a phosphate group,
For example, there may be mentioned a polymer having a minimum constitutional unit derived from a compound having one or more phosphoric acid groups and one or more polymerizable unsaturated groups in the molecule as a main constitutional component.

The minimum constitutional unit having an acidic group selected from the above (1) to (6), which constitutes the alkali-soluble resin, does not need to be only one kind, and the minimum constitutional unit having the same acidic group can be used. It is also possible to use a copolymer of two or more kinds, or two or more kinds of minimum constitutional units having different acidic groups.

The above-mentioned copolymer is copolymerized (1)-
A compound having an acidic group selected from (6) is preferably contained in the copolymer in an amount of 10 mol% or more, more preferably 20 mol% or more. 10 mol%
If it is less than 1, the developing latitude tends to be insufficiently improved.

In the present invention, when the compound is copolymerized and the alkali-soluble resin is used as the copolymer, as the compound to be copolymerized, the other compound containing no acidic group of the above (1) to (6) is used. You can also Examples of the other compounds (1) to (6) not containing an acidic group include the following (m1)
The compounds listed in (m12) to (m12) can be exemplified, but the invention is not limited thereto. (M1) Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate. (M2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
Alkyl acrylates such as hexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate and glycidyl acrylate. (M3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2-
Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, etc. (M4) acrylamide, methacrylamide, N-methylol acrylamide, N-ethyl acrylamide, N
-Hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N
-Acrylamide or methacrylamide such as phenylacrylamide, N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide.

(M5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether and phenyl vinyl ether. (M6) vinyl acetate, vinyl chloroacetate,
Vinyl esters such as vinyl butyrate and vinyl benzoate. (M7) Styrenes such as styrene, α-methylstyrene, methylstyrene and chloromethylstyrene. (M8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone. (M9) Olefins such as ethylene, propylene, isobutylene, butadiene and isoprene. (M10) N-vinylpyrrolidone, acrylonitrile,
Methacrylonitrile etc. (M11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, and N- (p-chlorobenzoyl) methacrylamide. (M12) An unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic anhydride or itaconic acid.

The alkali-soluble resin preferably has a phenolic hydroxyl group from the viewpoint of excellent image formability when exposed to an infrared laser or the like, and examples thereof include phenol formaldehyde resin, m-cresol formaldehyde resin and p-cresol formaldehyde resin. , M
Preference is given to novolak resins such as − / p-mixed cresol formaldehyde resin and phenol / cresol (m-, p-, or m- / p-mixed) mixed formaldehyde resin, and pyrogallolacetone resin.

Further, as the alkali-soluble resin having a phenolic hydroxyl group, further, US Pat. No. 4,123,
As described in Japanese Patent No. 279, there may be mentioned condensation polymers of phenol and formaldehyde having a C3-8 alkyl group as a substituent, such as t-butylphenol formaldehyde resin and octylphenol formaldehyde resin.

The weight average molecular weight of the alkali-soluble resin is preferably 500 or more from the viewpoint of image forming property, and more preferably 1,000 to 700,000. The number average molecular weight is preferably 500 or more, more preferably 750 to 650,000. The dispersity (weight average molecular weight / number average molecular weight) is preferably 1.1 to 10.

Further, these alkali-soluble resins may be used alone or in combination of two or more kinds. When combined, US Pat. No. 4,12
An alkyl group having 3 to 8 carbon atoms as a substituent, such as a polycondensation polymer of t-butylphenol and formaldehyde or a polycondensation polymer of octylphenol and formaldehyde as described in Japanese Patent No. 3,279. And a polycondensate of phenol and formaldehyde, and an alkali-soluble resin having a phenol structure having an electron-withdrawing group on the aromatic ring described in JP-A-2000-241972 previously filed by the present inventors. May be.

The total content of the alkali-soluble resin in the present invention is 30 to 9 in the total solid content of the image-forming material.
8 wt% is preferable, and 40 to 95 wt% is more preferable. When the content is less than 30% by weight, the durability tends to deteriorate, and when it exceeds 98% by weight, the sensitivity and the image forming property tend to decrease, which is not preferable.

[Infrared Absorber] In addition, an infrared absorbing agent known in the prior art may be used in combination with the interaction-releasing image-forming material for the purpose of improving the image-forming property unless the effects of the present invention are impaired. it can. The infrared absorbent that can be used in the present invention can be used without any limitation in the absorption wavelength range as long as it is a substance that absorbs the light energy radiation used for recording and generates heat. From the viewpoint of compatibility with output lasers, wavelengths from 760 nm to 12
An infrared absorbing dye or pigment having an absorption maximum at 00 nm is preferable.

As the dyes, commercially available dyes and known dyes described in documents such as "Handbook of Dyes" (edited by the Society of Synthetic Organic Chemistry, published in 1970) can be used. Specifically, azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinone imine dyes, methine dyes, cyanine dyes, squarylium dyes, pyrylium salts, metal thiolate complexes, oxonol dyes. , Dyes such as diimonium dyes, aminium dyes, and croconium dyes.

Preferred dyes are, for example, JP-A-5
Cyanine dyes described in JP-A No. 8-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60-78787, and JP-A-58-1736.
96, JP-A-58-181690, JP-A-58-1
Methine dyes described in Japanese Patent Application No. 94595, JP-A-Sho 5
8-112793, JP-A-58-224793, JP-A-59-48187, JP-A-59-73996,
Naphthoquinone dyes described in JP-A-60-52940, JP-A-60-63744 and the like, JP-A-58-1
Squarylium dyes described in No. 12792,
Examples thereof include cyanine dyes described in British Patent 434,875.

The near infrared absorption sensitizer described in US Pat. No. 5,156,938 is also preferably used, and the substituted arylbenzo (thio) described in US Pat. No. 3,881,924 is also used. Pyrylium salt, JP-A-57-142645
Trimethine thiapyrylium salt described in U.S. Pat. No. 4,327,169, JP-A Nos. 58-181051, 58-220143, 59-41363 and 59-11363.
-84248, 59-84249, 59-14
Nos. 6063 and 59-146061, pyranium compounds described in JP-A-59-216146, pentamethine thiopyrylium salts described in U.S. Pat. No. 4,283,475, and the like. Fair 5-13
The pyrylium compounds disclosed in Nos. 514 and 5-19702 are also preferably used.

Another preferable example of the dye is the compound of formula (I) in US Pat. No. 4,756,993.
The near infrared absorbing dye described as (II) can be mentioned.

Among these dyes, particularly preferable are cyanine dyes, phthalocyanine dyes, oxonol dyes, squarylium dyes, pyrylium salts, thiopyrylium dyes, and nickel thiolate complexes. Further, the dyes represented by the following general formulas (a) to (e) are preferable because they are excellent in photothermal conversion efficiency, and the cyanine dye represented by the following general formula (a) is used in the polymerizable composition of the present invention. In this case, it is most preferable because it gives a high polymerization activity and is excellent in stability and economy.

[0084]

[Chemical 9]

In the general formula (a), X ¹ represents a hydrogen atom, a halogen atom, —NPh ₂ , X ² —L ¹ or a group shown below. Here, X ² represents an oxygen atom or a sulfur atom, and L ¹
Represents a hydrocarbon group having 1 to 12 carbon atoms, an aromatic ring having a hetero atom, and a hydrocarbon group having 1 to 12 carbon atoms containing a hetero atom. Here, the hetero atom means N,
S, O, a halogen atom and Se are shown.

[0086]

[Chemical 10]

R ¹ and R ² each independently represent a hydrocarbon group having 1 to 12 carbon atoms. From the storage stability of the photosensitive layer coating liquid, R ¹ and R ² are preferably hydrocarbon groups having 2 or more carbon atoms, and further, R ¹ and R ² are bonded to each other to form a 5-membered ring or It is particularly preferable to form a 6-membered ring.

Ar ¹ and Ar ² may be the same or different and each represents an aromatic hydrocarbon group which may have a substituent. Preferred aromatic hydrocarbon groups include a benzene ring and a naphthalene ring. Moreover, as a preferable substituent, a hydrocarbon group having 12 or less carbon atoms,
Examples thereof include a halogen atom and an alkoxy group having 12 or less carbon atoms. Y ¹ and Y ² may be the same or different and each represents a sulfur atom or a dialkylmethylene group having 12 or less carbon atoms. R ³ and R ^{4, which} may be the same or different, each represents a hydrocarbon group having 20 or less carbon atoms, which may have a substituent. Preferred substituents include an alkoxy group having 12 or less carbon atoms, a carboxyl group and a sulfo group. R ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the availability of raw materials, hydrogen atom is preferable. Also, Za
^- represents a counter anion. However, when any of R ^{1 to} R ⁸ is substituted with a sulfo group, Za ⁻ is not necessary. Preferred Za ⁻ is a halogen ion, a perchlorate ion, a tetrafluoroborate ion, a hexafluorophosphate ion, from the storage stability of the photosensitive layer coating solution.
And a sulfonate ion, particularly preferably a perchlorate ion, a hexafluorophosphate ion, and an arylsulfonate ion.

Specific examples of the cyanine dye represented by the general formula (a) which can be preferably used in the present invention include those shown below and Japanese Patent Application No. 11-31062.
Paragraph numbers [0017] to [0019] of the specification No. 3 and paragraph number [001] of the specification of Japanese Patent Application No. 2000-224031.
2] to [0038], and those described in paragraph Nos. [0012] to [0023] of Japanese Patent Application No. 2000-211147.

[0090]

[Chemical 11]

[0091]

[Chemical 12]

[0092]

[Chemical 13]

[0093]

[Chemical 14]

[0094]

[Chemical 15]

In the general formula (b), L represents a methine chain having a conjugated carbon atom number of 7 or more, and the methine chain may have a substituent, and the substituents are bonded to each other to form a ring structure. You may have. Zb ⁺ represents a counter cation. Preferred counter cations include ammonium, iodonium, sulfonium, phosphonium, pyridinium, alkali metal cations (Ni ⁺ , K ⁺ , Li ⁺ ) and the like. R ⁹ ~
R ¹⁴ and R ^{15 to} R ²⁰ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. It represents a substituent selected from the group or a substituent in which two or three of them are combined, and may be bonded to each other to form a ring structure. Here, in the general formula (b), L represents a methine chain having 7 conjugated carbon atoms, and R ^{9 to} R ¹⁴ and R ^{15 to} R ²⁰ all represent hydrogen atoms, which are easily available. It is preferable from the viewpoint of the effect.

In the present invention, specific examples of the dye represented by formula (b) which can be preferably used include the followings.

[0097]

[Chemical 16]

[0098]

[Chemical 17]

In the general formula (c), Y ³ and Y ⁴ each represent an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom. M represents a methine chain having a conjugated carbon number of 5 or more.
R ^{21 to} R ²⁴ and R ^{25 to} R ²⁸ may be the same or different and each is a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, a carbonyl group or a thiol group. Represents a group, a sulfonyl group, a sulfinyl group, an oxy group, or an amino group. Also, in the formula Z
a ^- represents a counter anion, Z in the general formula (a)
a ^- as synonymous.

In the present invention, specific examples of the dye represented by formula (c) which can be preferably used include the followings.

[0101]

[Chemical 18]

[0102]

[Chemical 19]

In the general formula (d), R²⁹Through R³¹Is each
Independently represent a hydrogen atom, an alkyl group, or an aryl group.
You R³³And R³⁴Are each independently an alkyl group or a substituted
Represents a hydrogen atom or a halogen atom. n and m are independent of each other
An integer of 0 to 4 is shown. R ²⁹And R³⁰, Or R³¹And R³²
Each may combine with each other to form a ring, and R²⁹as well as
/ Or R³⁰Is R³³And again R³¹And / or R³²Is R³⁴When
May combine with each other to form a ring, and further, R³³Or R³⁴But
If there are multiple R³³Each other or R³⁴Each other
To form a ring. X¹And X²Each is independent
A hydrogen atom, an alkyl group, or an aryl group, and X
¹And X²At least one of which is a hydrogen atom or an alkyl group
Show. Q is a trimethine group which may have a substituent or
It is a pentamethine group and has a ring structure together with a divalent organic group.
You may form. Zc^-Represents a counter anion, and
Za in formula (a)^-Is synonymous with.

Specific examples of the dye represented by the general formula (d) which can be preferably used in the invention include the followings.

[0105]

[Chemical 20]

[0106]

[Chemical 21]

In the general formula (e), R ^{35 to} R ⁵⁰ are each independently a hydrogen atom which may have a substituent, a halogen atom, a cyano group, an alkyl group, an aryl group, an alkenyl group, an alkynyl group, A hydroxyl group, a carbonyl group, a thio group, a sulfonyl group, a sulfinyl group, an oxy group, an amino group, and an onium salt structure are shown. M represents two hydrogen atoms or a metal atom, a halometal group, or an oxymetal group. The metal atoms contained therein are IA, IIA of the periodic table,
IIIB, IVB group atoms, transition metals of the first, second and third periods, and lanthanoid elements are mentioned, and among them, copper, magnesium, iron, zinc, cobalt, aluminum, titanium and vanadium are preferable.

Specific examples of the dye represented by formula (e) which can be preferably used in the present invention include the followings.

[0109]

[Chemical formula 22]

Examples of the pigment used as the infrared absorber in the present invention include commercially available pigments and color index (CI) handbook, "Latest pigment handbook" (edited by Japan Pigment Technology Association, 1977), "Latest Pigment". Applied Technology "(CMC
Published in 1986), "Printing Ink Technology" published by CMC, published in 1984).

The types of pigments include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments,
Blue pigment, green pigment, fluorescent pigment, metal powder pigment, etc.
Polymer bound dyes may be mentioned. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments,
Perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, dyed lake pigments,
Azine pigment, nitroso pigment, nitro pigment, natural pigment, fluorescent pigment, inorganic pigment, carbon black and the like can be used.
Preferred among these pigments is carbon black.

These pigments may be used without surface treatment, or may be used after surface treatment. The surface treatment method includes a method of surface-coating a resin or wax, a method of attaching a surfactant, a method of binding a reactive substance (for example, a silane coupling agent, an epoxy compound, polyisocyanate, etc.) to the pigment surface, etc. Can be considered. The above surface treatment method is "property and application of metal soap" (Koushobo),
It is described in "Printing Ink Technology" (CMC Publishing, 1984) and "Latest Pigment Application Technology" (CMC Publishing, 1986).

The particle size of the pigment is preferably in the range of 0.01 μm to 10 μm, more preferably in the range of 0.05 μm to 1 μm, and particularly preferably in the range of 0.1 μm to 1 μm. Particle size of pigment is 0.01μm
If it is less than 10 μm, it is not preferable from the viewpoint of stability of the dispersion in the coating liquid for the image-sensitive layer, and if it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the image-sensitive layer.

As a method for dispersing the pigment, a known dispersion technique used in ink production, toner production and the like can be used. Examples of the disperser include an ultrasonic disperser, a sand mill, an attritor, a pearl mill, a super mill, a ball mill, an impeller, a disperser, a KD mill, a colloid mill, a dynatron, a three-roll mill and a pressure kneader. For details, see "Latest Pigment Application Technology" (CMC Publishing, 1
986).

When these pigments or dyes are added, the amount is 0.01 to 0.01 based on the total solid content of the image forming material.
It may be added in an amount of 50% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 10% by weight in the case of a dye, and particularly preferably 0.1 to 10% by weight in the case of a pigment. If the addition amount of the pigment or dye is less than 0.01% by weight, the effect of improving the sensitivity is lowered, and if it exceeds 50% by weight, the uniformity of the photosensitive layer is lost and the durability of the image forming material is deteriorated.

<Acid-catalyzed Decomposition System> The acid-catalyzed decomposition system image-forming material is formed by the action of the above-mentioned (a) infrared-absorbing oligomer, heat (a) efficiently generated by the infrared-absorbing oligomer, or light. An essential component is a compound that generates an acid (acid generator), and a compound that cleaves a chemical bond by using the generated acid as a catalyst to increase the solubility in an alkaline developer (acid decomposable compound). Due to such a mechanism of acid-catalyzed decomposition, the acid-catalyzed decomposition image-forming material is also referred to as a chemically amplified image-forming material.

The acid-catalyzed decomposition type image-forming material is further provided with a high-molecular compound (for example, the high-molecular compound soluble in an alkaline aqueous solution (b) mentioned above) which is a binder component for forming the image-forming material and a sensitivity improvement. The desired infrared absorber may be contained, and the acid-decomposable compound itself may be a polymer compound or a precursor thereof that functions as a binder component. When the acid-catalyzed decomposition type image-forming material is used in combination with a plurality of image-forming materials as one layer in the multilayer structure, it is particularly preferably formed on the exposed surface as the uppermost layer.

[Acid-decomposable compound] In the present invention, a compound that cleaves a chemical bond with an acid as a catalyst to increase the solubility in an alkali developing solution is a compound having a bond group capable of decomposing with an acid in the molecule. It can be replaced. Such a compound is described in JP-A No. 9-171254, "(b) Compound having at least one decomposable bond with an acid".
Can be used. The coupling capable of being decomposed by an acid, for _{example, - (CH 2 CH 2 O} ) n -
A group (n represents an integer of 2 to 5) and the like can be preferably mentioned. Among such compounds, it is preferable to use the compound represented by the following general formula (1) from the viewpoint of sensitivity and developability.

[0119]

[Chemical formula 23]

[In the formula, R, R ¹ and R ² are each a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms.
Represents an alkoxy group, a sulfo group, a carboxyl group or a hydroxyl group, p, q and r each represent an integer of 1 to 3, and m and n each represent an integer of 1 to 5. ]

In the general formula (1), the alkyl group represented by R, R ¹ and R ² may be linear or branched, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and a tert-butyl group. , A pentyl group and the like, and examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group,
Examples thereof include a tert-butoxy group and a pentoxy group, and the sulfo group and the carboxyl group include salts thereof. Among the compounds represented by the general formula (1), compounds in which m and n are 1 or 2 are particularly preferable. The compound represented by the general formula (1) can be synthesized by a known method.

Other acid-decomposable compounds applicable to the present invention are JP-A-48-89603 and 51-12.
0714, 53-333429, 55-129.
No. 95, No. 55-126236, No. 56-17345.
Compounds having C--O--C bond described in JP-A-60-
-37549, Si described in No. 60-12146
Compound having --O--C bond, JP-A-60-3625
Other acid-decomposable compounds described in JP-A No. 60-10247 and JP-A No. 62-22 can be mentioned.
2246, compounds having a Si-N bond, carbonic acid esters described in JP-A-62-251743, orthocarbonic acid esters described in JP-A-62-209451, JP-A-62 -280841 orthotitanate, JP-A-62-
Orthosilicic acid esters described in JP-A No. 280842, JP-A No. 63-0101053, and JP-A No. 9-1712.
No. 54, No. 10-55067, No. 10-111564.
No. 10-87733, No. 10-153853,
No. 10-228102, No. 10-268507, No. 282648, No. 10-282670, EP-08.
84547 Al, acetals, ketals and orthocarboxylic acid esters, JP-A-64-2440.
The compound having a C—S bond described in No. 38 can be used.

Among the above acid-decomposable compounds, JP-A-53-133429, JP-A-56-17345 and JP-A-56-17345 are particularly preferable.
-121446, 60-37549, and 62-2
09451, 63-0101053, JP-A-9-1
71254, 10-55067, 10-111.
No. 564, No. 10-87733, No. 10-15385.
No. 3, No. 10-228102, No. 10-268507
No. 282648, No. 10-282670, EP
0884647Al C-O-described in each specification
Compounds having a C bond, compounds having a Si—O—C bond, orthocarbonates, acetals, ketals and silyl ethers are preferable. Among these acid-decomposable compounds, a polymer compound having an acetal or ketal moiety in the main chain repeatedly and whose solubility in an alkaline developer is increased by the acid generated is preferably used.

These acid-decomposable compounds may be used alone or in combination of two or more. The amount of addition is 5 to 70% by weight, preferably 10 to 50% by weight, more preferably 15% by weight based on the total solid content of the chemical amplification layer.
It is added to the layer in a proportion of ˜35% by weight. If the addition amount is less than 5% by weight, stains on non-image areas are likely to occur,
On the other hand, if the addition amount exceeds 70% by weight, the film strength of the image area becomes insufficient, which is not preferable.

Examples of the negative type image forming material include radical polymerization type and acid catalyst cross-linking type (including cationic polymerization). These are described below in order.

<Radical Polymerization System> The radical polymerization system image-forming material of the present invention comprises the above-mentioned (a) infrared-absorbing oligomer and (a) heat or light efficiently generated by the infrared-absorbing oligomer. Containing a compound that generates a radical (hereinafter referred to as a radical generator) and a compound capable of radical polymerization (referred to as a polymerizable compound),
For example, by irradiation with an infrared laser or the like, radicals are generated from the radical generator in the exposed area, which serves as an initiator, and the polymerizable compound is cured by a radical polymerization reaction to form an image area. The combination of the radical generator and the polymerizable compound used here may be appropriately selected from known ones as long as the strength of the film formed by radical polymerization satisfies the requirements as an image forming material. it can. Further, in order to improve the reactivity of the radical generator, an accelerator such as an onium salt or a reducing agent may be used in combination. Examples of components that can be used in the radically polymerized layer include compounds described as constituent components of thermopolymerizable image-forming materials in JP-A-8-108621, and those of image-forming materials in JP-A-9-34110. The compounds described as the constituents can also be preferably used.

(Radical Generator) As the radical generator used in the radical polymerization type image forming material, known radical polymerization initiators generally used in polymer synthesis reaction by radical polymerization can be used without particular limitation. , 2,2'-azobisisobutyronitrile, 2,2 '
-Azobisnitrile compounds such as azobispropionitrile, benzoyl peroxide, lauroyl peroxide, acetyl peroxide, -t-butyl perbenzoate, α-cumylhydroperoxide, di-t-butyl peroxide, Organic peroxides such as diisopropyl peroxy dicarbonate, t-butyl peroxy isopropyl carbonate, peracids, alkyl peroxy carbamates and nitrosoaryl acylamines, and inorganic peroxides such as potassium persulfate, ammonium persulfate and potassium perchlorate. Oxides, azo or diazo compounds such as diazoaminobenzene, p-nitrobenzenediazonium, azobis-substituted alkanes, diazothioethers and arylazosulfones, nitrosophenylurea, tetraalkylthiuram such as tetramethylthiuram disulfide Arm disulfides, diaryl disulfides such as dibenzoyl disulfide, dialkyl xanthate disulfides, aryl sulfinic acids, arylalkyl sulfones include a 1-alkanoic sulfinic acids and the like.

When the radical-polymerization type image-forming material of the present invention is recorded by an infrared laser, the temperature reached on the exposed surface becomes 600 ° C. or more, depending on the energy of the laser, so that radicals having large activation energy are generated. A sufficient sensitivity can be obtained with an agent. The activation energy for radical generation of the radical generator is preferably 30 kcal / mol or more, and examples thereof include azobisnitrile compounds and organic peroxides. Above all, it has excellent stability at room temperature and a high decomposition rate when overheated,
A compound that becomes colorless upon decomposition is preferable, and examples thereof include benzoyl peroxide and 2,2′-azobisisobutyronitrile. Even if the above radical generator is used alone, 2
One or more species may be used in combination, and about 0.5 to 30% by weight, preferably 2 to 10% by weight, based on the total solid content of the radical polymerization layer.
Used in.

Further, a compound which generates a radical by the interaction with an onium salt described later can also be preferably used. Specifically, halides (α-haloacetophenones, trichloromethyltriazines, etc.), azo compounds, aromatic carbonyl compounds (benzoin esters, ketals, acetophenones, o-acyloxyimino ketones, acylphosphine oxides) etc),
Hexaarylbisimidazole compounds, peroxides and the like can be mentioned, but preferably, the above-mentioned JP-A-9-3411.
Examples of the bisimidazole derivatives disclosed as (A-1) to (A-4) on page 16 of JP-A-No. The latter radical generator achieves high sensitivity by interaction with an onium salt. Examples of onium salts that can be used in combination with this radical generator include paragraphs [0022] to
Examples thereof include phosphonium salt, sulfonium salt, iodonium salt, and ammonium salt compounds described in [0049].

The addition amount of the onium salt varies depending on the type and usage of the onium salt, but is preferably 0.05 to 50% by weight based on the total solid content of the image forming material. In addition, (acid generator) in <acid catalyst cross-linking system> described later
Iodonium salts, sulfonium salts, phosphonium salts, onium salts such as diazonium salts, which can be preferably used as, can be used alone as a radical generator without using together with the radical generator, and the addition amount thereof is The amount is preferably 0.05 to 50% by weight with respect to the total solid content of the image forming material, although it varies depending on the type and use form.

(Polymerizable Compound) As the polymerizable polymer compound which is polymerized and cured by the radicals generated from the radical generator, known monomers having a polymerizable group can be used without particular limitation. Specific examples of such a monomer include 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, and 2-ethylhexyl acrylate.
Monofunctional acrylic acid esters such as hydroxypropyl acrylate and their derivatives or compounds obtained by replacing these acrylates with methacrylate, itaconate, crotonate, maleate, etc .; polyethylene glycol diacrylate, pentaerythritol diacrylate, bisphenol A diacrylate, hydroxypivalic acid neo Bifunctional acrylic acid esters such as diacrylates of ε-caprolactone adduct of pentyl glycol and their derivatives or compounds in which these acrylates are replaced with methacrylates in the same manner as described above; or trimethylolpropane tri (meth) acrylate, dipentaerythritol Polyfunctional acrylics such as pentaacrylate, dipentaerythritol hexaacrylate, and pyrogallol triacrylate Compounds ester and their derivatives or their acrylate is replaced with methacrylate, and the like. Further, a so-called prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerization property can also be suitably used.

In addition to this, JP-A-58-212994,
61-6649, 62-46688, 62-
48589, 62-173295, 62-18.
7092, 63-67189, JP-A-1-244.
Compounds described in No. 891 and the like can be mentioned, and further, “11290 chemical products”, Chemical Industry Daily, 286-
The compounds described on page 294, the compounds described on pages 11 to 65 of "UV / EB curing handbook (raw material edition)", Kobunshi Kogyo Kai, etc. can also be preferably used.

Of these, compounds having two or more acryl groups or methacryl groups in the molecule are preferable in the present invention, and those having a molecular weight of 10,000 or less, more preferably 5,000 or less are desirable. In the present invention, the polymerizable compound is a monomer having a polymerizable group, including those exemplified above, or a prepolymer, and if there is no problem with one kind or compatibility or compatibility depending on the purpose,
Two or more kinds can be used in combination. The compound having an ethylenically unsaturated group is preferably 20 to 80% by weight, more preferably 30% by weight as a solid content in the image forming material.
-60% by weight.

(Binder Resin) It is preferable to use a binder resin for the radical polymerization type image forming material from the viewpoint of improving the film property. As the binder resin, the above-mentioned (b) polymer compound soluble in an alkaline aqueous solution can be used, as well as polyester resin, polyvinyl acetal resin, polyurethane resin, polyamide resin, cellulose resin, olefin resin. Resin, vinyl chloride resin, (meth) acrylic resin, styrene resin, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, polysulfone, polycaprolactone resin, polyacrylonitrile resin, urea resin, epoxy resin, phenoxy resin, rubber resin, etc. Can be mentioned. Further, a resin having an unsaturated bond in the resin, for example, a diallyl phthalate resin and its derivative, chlorinated polypropylene, etc., can be polymerized with the above-mentioned compound having an ethylenically unsaturated bond, so that it is suitably used depending on the application. Can be used. As the binder resin, one kind or a combination of two or more kinds of the above-mentioned resins can be used. These binder resins are used in an amount of 500 parts by weight or less, more preferably 200 parts by weight or less, based on 100 parts by weight of the polymerizable compound.
It is preferably used in the range of not more than parts by weight. By adding the specific infrared absorbing agent to such a radical polymerization type image forming material, the sensitivity can be improved and the radical polymerization reaction can be promoted.

(Other Compounds) Various additives used in combination with conventionally known photopolymerizable compounds can be appropriately used in the radical polymerization type image forming material. A thermal polymerization inhibitor is mentioned as an additive. Specifically, hydroquinone, pyrogallol, p-methoxyphenol, catechol, β-
Examples include naphthol, quinone-based compounds such as 2,6-di-t-butyl-p-cresol, and phenol-based compounds, and a total of 100 parts by weight of the polymerizable compound having an ethylenically unsaturated bond and the binder resin, It is used in an amount of 10 parts by weight or less, preferably about 0.01 to 5 parts by weight. In addition, the above infrared absorber may be added to improve the sensitivity.

Examples of compounds that can be added as oxygen quenchers include N, N-dialkylaniline derivatives such as the compounds described in US Pat. No. 4,772,541 at column 11, line 58 to column 12, line 35. Can be mentioned. Further, in order to improve the film quality, a plasticizer can be used, and for example, phthalic acid esters, trimellitic acid esters,
Adipic acid esters, other saturated or unsaturated carboxylic acid esters, citric acid esters, epoxidized soybean oil, epoxidized linseed oil, stearic acid epoxys, orthophosphoric acid esters, phosphorous acid esters, glycol esters, etc. Is mentioned.

It is also preferable to use an acid generator in combination as an additive that generates an acid by heating and accelerates the decomposition of the radical generator. As the acid generator, those described in detail in the following explanation of the acid-catalyzed crosslinking system image forming material can be used. A lithographic printing plate precursor using a radical polymerization type image forming material as a recording layer forms a radical polymerization type recording layer by appropriately selecting the above components, dissolving them in a suitable solvent and coating them on a support. However, the coating amount after drying is preferably about 0.01 to 5.0 g / m ² .

When a radical polymerization type image forming material is used for the recording layer, an oxygen impermeable overcoat layer may be provided adjacent to the recording layer in order to prevent polymerization inhibition by oxygen. Materials for the overcoat layer include polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose,
A water-soluble resin such as polyvinylpyrrolidone is preferable, and a film thickness of about 0.2 to 3 μm is suitable. If necessary, a dye or pigment that does not absorb light from the light source used for recording may be added to the overcoat layer as a filter agent.

<Acid-Catalyst Crosslinking System> The acid-catalyst crosslinking system image-forming material of the present invention includes the above-mentioned (a) infrared-absorbing oligomer, heat generated by the (a) infrared-absorbing oligomer, or Contains a compound that generates an acid by light (hereinafter, referred to as an acid generator) and a compound that can be crosslinked by using the generated acid as a catalyst (hereinafter, referred to as a crosslinker), and further forms a layer containing these To this end, a binder polymer capable of reacting with the crosslinking agent in the presence of an acid is included. In this acid-catalyzed cross-linking image-forming material, the acid generated by decomposition of the acid generator by light irradiation or heating promotes the function of the cross-linking agent, and the cross-linking agents themselves or between the cross-linking agent and the binder polymer are mixed. A strong crosslinked structure is formed, which reduces alkali solubility and makes the developer insoluble.

As the acid-catalyst cross-linking type image forming material having such characteristics, known constituent components of layers having similar characteristics can be used. For example, JP-A-7-206
The compounds described as the components of the layer composed of a radiation-sensitive composition containing a resole resin, a novolac resin, a latent Bronsted acid, and an infrared absorber described in JP-A No. 29-29 are cited. Here, the "latent Bronsted acid" refers to a precursor that decomposes to produce Bronsted acid, and is a compound having both properties of the acid generator and the acid crosslinking agent in the present invention. Bronsted acids are believed to catalyze the matrix-forming reaction between resole resins and novolac resins, and examples of suitable Bronsted acids for this purpose are trifluoromethanesulfonic acid and hexafluorophosphonic acid.

Further, ionic latent Bronsted acids are preferred, examples of which include onium salts, especially iodonium, sulfonium, phosphonium, selenonium, diazonium, and arsonium salts. Nonionic latent Bronsted acids can also be preferably used. For example, the following compounds: RCH ₂ X, RCHX ₂ , R
CX ₃ , R (CH ₂ X) ₂ , and R (CH ₂ X) ₃ , (wherein, X is Cl, Br, F, or CF ₃ , SO ₃ , and R is an aromatic group or a fat. Which is a combination of a group or an aromatic group and an aliphatic group).

Further, an image forming material containing an acid crosslinkable compound and a high molecular weight binder described in JP-A No. 11-95415 is also preferable. This is a compound capable of generating an acid upon irradiation with an actinic ray, for example, a salt such as diazonium, phosphonium, sulfonium, and iodonium, an organic halogen compound, orthoquinone-
A compound having at least one bond capable of being crosslinked with diazidosulfonyl chloride and an organometallic / organohalogen compound in the presence of the acid, for example, an alkoxymethyl group, a methylol group, an acetoxymethyl group or the like as a functional group. Individual amino compounds, at least two-substituted aromatic compounds having an alkoxymethyl group, a methylol group, an acetoxymethyl group, etc. as functional groups, resole resins and furan resins, acrylic resins synthesized from specific monomers, and the like. It is a photosensitive layer containing and can be used.

The acid-catalyzed crosslinking system image-forming material of the present invention comprises
Included are acid generators, crosslinkers and binder polymers, and the like, but these compounds will now be described individually. (Acid Generator) In the present invention, the compound (acid generator) which generates an acid by light or heat means irradiation with infrared rays or 100 ° C.
It means a compound that decomposes to generate an acid by the above heating.
As the acid generated, pKa of sulfonic acid, hydrochloric acid, etc. is 2
The following strong acids are preferred.

Examples of the acid generator preferably used in the present invention include onium salts such as iodonium salts, sulfonium salts, phosphonium salts and diazonium salts.
Specifically, US Pat. No. 4,708,925 and JP-A-7-2
The compounds described in No. 0629 can be mentioned. Particularly, iodonium salts, sulfonium salts, and diazonium salts having sulfonate ion as a counter ion are preferable.
Examples of diazonium salts include U.S. Pat. No. 3,867,14.
Diazonium compounds described in US Pat. No. 2,631.
The diazonium compounds described in JP-A No. 2,703 and the diazo resins described in JP-A-1-102456 and JP-A-1-102457 are also preferable. Also, U
The benzyl sulfonates described in S5,135,838 and US5,200,544 are also preferable. Furthermore, JP-A Nos. 2-100054 and 2-10005.
The active sulfonic acid esters and disulfonyl compounds described in JP-A No. 5 and JP-A No. 9-197671 are also preferable. In addition, haloalkyl-substituted S-triazines described in JP-A-7-271029 are also preferable.

These acid generators are contained in an amount of 0.01 to 50% by weight, preferably 0.1 to 40% by weight, and more preferably 0.5 to 30% by weight based on the total solid content of the acid-catalyzed crosslinking image-forming material.
It is added to the acid cross-linking layer in a weight percentage. Addition amount is 0.
If it is less than 01% by weight, an image cannot be obtained. On the other hand, if the addition amount exceeds 50% by weight, stains are generated on the non-image area during printing.

These compounds may be used alone,
Moreover, you may use it in combination of 2 or more type. Since the acid generators mentioned here can be decomposed by irradiation of ultraviolet rays, the image recording can be performed not only by irradiation of infrared rays but also by irradiation of ultraviolet rays by using the image forming material having such a form.

(Acid Crosslinking Agent) The crosslinking agent that can be used in the acid-catalyzed crosslinking image-forming material of the present invention is not particularly limited as long as it is a compound that crosslinks with an acid, and is represented by the following general formula (I). Phenol derivative (hereinafter, appropriately referred to as low molecular weight phenol derivative), polynuclear having 3 or more phenol rings having 2 or 3 hydroxymethyl groups on the ring represented by the following general formula (II) A type phenolic crosslinking agent, a mixture of the low molecular weight phenol derivative and a polynuclear type phenolic crosslinking agent and / or a resole resin, and the like are preferably used.

[0148]

[Chemical formula 24]

In the formula, Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. R ¹ and R ^{2, which} may be the same or different, each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. R ³ represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. m represents an integer of 2 to 4. n shows the integer of 1-3. X represents a divalent linking group, Y represents a monovalent to tetravalent linking group having the above partial structure or a functional group whose terminal is a hydrogen atom, and Z is present when Y is a terminal group. Or a monovalent to tetravalent linking group or a functional group existing depending on the number of Y linking groups.

[0150]

[Chemical 25]

In the formula, A represents an r-valent hydrocarbon linking group having 1 to 20 carbon atoms, and r represents an integer of 3 to 20. p is
An integer of 2-3 is shown. Regarding the phenol derivative represented by the general formula (I), the applicant of the present application has previously filed Japanese Patent Application No. 11-352210, paragraph number [0098] to
As described in detail in [0155], the polynuclear phenolic cross-linking agent represented by the general formula (II) and having 3 or more phenol rings having 2 or 3 hydroxymethyl groups on the ring in the molecule Also, paragraph number [0156] of the same specification
~ [0165].

These crosslinking agents may be used alone,
Moreover, you may use it in combination of 2 or more types. In the present invention, the crosslinking agent is used in an amount of 5 to 70% by weight, preferably 10 to 65% by weight, based on the solid content of the acid-catalyzed crosslinking system image forming material. If the addition amount of the cross-linking agent is less than 5% by weight, the film strength of the image area when recording an image is deteriorated, and
If it exceeds 70% by weight, it is not preferable in terms of stability during storage.

Examples of the binder polymer that can be used in the acid-catalyzed crosslinking image-forming material of the present invention include polymers having an aromatic hydrocarbon ring to which a hydroxy group or an alkoxy group is directly bonded, in the side chain or main chain. The alkoxy group preferably has 20 or less carbon atoms from the viewpoint of sensitivity. Further, as the aromatic hydrocarbon ring, a benzene ring, a naphthalene ring or an anthracene ring is preferable from the availability of raw materials. These aromatic hydrocarbon rings have a substituent other than a hydroxy group or an alkoxy group, for example, a halogen group,
Although it may have a substituent such as a cyano group, it is preferable that it has no substituent other than the hydroxy group or the alkoxy group from the viewpoint of sensitivity.

The binder polymer which can be preferably used in the acid-catalyzed crosslinking image-forming material of the present invention is
It is a polymer having a structural unit represented by the following general formula (III) or a phenol resin such as a novolac resin.

[0155]

[Chemical formula 26]

In the formula, Ar ² represents a benzene ring, a naphthalene ring or an anthracene ring. R ⁴ represents a hydrogen atom or a methyl group. R ⁵ represents a hydrogen atom or an alkoxy group having 20 or less carbon atoms. X ¹ is a single bond or C, H,
It represents a divalent linking group having 0 to 20 carbon atoms and containing at least one atom selected from N, O and S. k represents an integer of 1 to 4.

In the present invention, as the binder polymer,
A homopolymer consisting only of the structural unit represented by the general formula (III) may be used, but with this specific structural unit,
A copolymer having a structural unit derived from another known monomer may be used. The proportion of the structural unit represented by the general formula (III) contained in the copolymer using these is
The amount is preferably 50 to 100% by weight, more preferably 60 to 100% by weight.

The weight average molecular weight of the binder polymer that can be used is preferably 5,000 or more,
The range is more preferably 10,000 to 300,000, the number average molecular weight is preferably 1,000 or more, and more preferably 2,000 to 250,000. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 to 10. These binder polymers may be random polymers, block polymers, graft polymers, etc., but are preferably random polymers.

Next, the novolaks will be described. Examples of the novolak resin preferably used in the present invention include phenol novolak, o-, m-, p-various cresol novolaks, and copolymers thereof, and halogen-based novolaks using phenol substituted with an alkyl group. To be The weight average molecular weight of these novolac resins is preferably 1,000 or more, more preferably 2,000.
It is in the range of 0 to 20,000, and the number average molecular weight is preferably 10
00 or more, more preferably 2,000 to 15,0
The range is 00. The polydispersity is preferably 1 or more, more preferably 1.1 to 10.

It is also a preferred embodiment to use, as the binder polymer, a polymer having a heterocyclic group having an unsaturated bond in the ring. Here, the term “heterocycle” refers to one in which at least one heteroatom other than carbon is included in the atoms constituting the ring system. The hetero atom used is preferably a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom. It is considered that the use of the polymer having such a heterocyclic group facilitates the chemical structural reaction due to the function of the lawn pair existing in the present heterocycle, and forms a film having good printing durability.

The binder polymers used in the present invention described above may be used alone or in combination of two or more kinds. These polymers are contained in an amount of 20 to 95% by weight, preferably 40% by weight, based on the total solid content of the acid-catalyzed crosslinking image-forming material.
~ 90 wt% is added. 20% by weight
When it is less than the above, the strength of the image portion is insufficient when the image is formed. If the addition amount exceeds 95% by weight, no image is formed.

Also in this acid-catalyzed cross-linking image-forming material, the sensitivity can be improved by containing the above infrared absorber. When forming the acid-catalyzed crosslinkable image-forming material, various additives such as a surfactant can be used together for the purpose of improving coatability and film quality.

The positive type and negative type image forming materials have been described above. However, unless otherwise specified, each image forming material may optionally include the above-mentioned (b) a polymer compound soluble in an alkaline aqueous solution. As the binder polymer, the above infrared absorber can be used for the purpose of improving sensitivity.

[Other Components] The above-described positive-working and negative-working image-forming materials of the present invention may further contain, if necessary.
Various additives can be added. For example, addition of other onium salt, aromatic sulfone compound, aromatic sulfonic acid ester compound, polyfunctional amine compound, etc. improves the function of preventing dissolution of alkali water-soluble polymer (alkali-soluble resin) in the developer. Is preferable because it can

Examples of the onium salt include diazonium salt, ammonium salt, phosphonium salt, iodonium salt, sulfonium salt, selenonium salt and arsonium salt. The onium salt is preferably added in an amount of 1 to 50% by weight, more preferably 5 to 30% by weight, particularly preferably 10 to 30% by weight, based on the total solid content of the image forming material. preferable.

Further, cyclic acid anhydrides, phenols, and organic acids may be used in combination for the purpose of improving sensitivity. As the cyclic acid anhydride, US Pat. No. 4,11
5,128, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
3,6-endooxy-Δ4-tetrahydrophthalic anhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleic anhydride, α-phenylmaleic anhydride, succinic anhydride, pyromellitic anhydride and the like can be used. Examples of phenols include bisphenol A, p-nitrophenol, p-ethoxyphenol, 2,4,4'-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 4-hydroxybenzophenone,
4,4 ', 4 "-trihydroxytriphenylmethane, 4,4', 3", 4 "-tetrahydroxy-
3,5,3 ', 5'-tetramethyltriphenylmethane and the like can be mentioned. Further, as organic acids, Japanese Patent Laid-Open No.
Examples thereof include sulfonic acids, sulfinic acids, alkylsulfuric acids, phosphonic acids, phosphoric acid esters and carboxylic acids described in 0-88942 and JP-A-2-96755. The proportion of the above cyclic acid anhydride, phenols and organic acids in the image forming material is preferably 0.05 to 20% by weight, more preferably 0.1 to 15% by weight, particularly preferably 0.1 to 15% by weight. It is 10% by weight.

In addition to these, epoxy compounds,
Vinyl ethers, further, a phenol compound having a hydroxymethyl group described in JP-A-8-276558, a phenol compound having an alkoxymethyl group, and a phenol compound described in JP-A-11-160860 previously proposed by the present inventors. A crosslinkable compound or the like having an alkali dissolution suppressing action can be appropriately added depending on the purpose.

Further, in the image-forming material of the present invention, in order to enhance the stability of processing against developing conditions, JP-A-62-251740 and JP-A-3-208514 are used.
Nonionic surfactants as described in JP-A-59-121044 and JP-A-4-13149.
Amphoteric surfactants such as those described in the publication can be added.

In the image-forming material of the present invention, a printing-out agent for obtaining a visible image immediately after heating by exposure,
Dyes or pigments as image colorants can be added.
A typical example of the print-out agent is a combination of a compound that releases an acid when heated by exposure (photo-acid releasing agent) and an organic dye capable of forming a salt. In particular,
A combination of an o-naphthoquinonediazide-4-sulfonic acid halogenide and a salt-forming organic dye described in JP-A-50-36209 and JP-A-53-8128, and JP-A-53-36223 and JP-A-53-36223. 54-74728, 6
0-3626, 61-143748, 61-1
There may be mentioned combinations of trihalomethyl compounds and salt-forming organic dyes described in JP-A-51644 and JP-A-63-58440. Such trihalomethyl compounds include oxazole-based compounds and triazine-based compounds, both of which have excellent stability over time and give a clear printout image.

As the image colorant, other dyes can be used in addition to the above-mentioned salt-forming organic dyes. Suitable dyes include oil-soluble dyes and basic dyes, including salt-forming organic dyes. Specifically, Oil Yellow # 101, Oil Yellow # 103, Oil Pink #
312, Oil Green BG, Oil Blue BOS, Oil Blue # 603, Oil Black BY, Oil Black BS, Oil Black T-505 (all manufactured by Orient Chemical Industry Co., Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), Methyl. Violet (CI42535), ethyl violet, Rhodamine B (CI145170B), malachite green (CI42000), methylene blue (CI5201).
5) etc. can be mentioned. In addition, JP-A-62-2
The dyes described in Japanese Patent No. 93247 are particularly preferable. These dyes are based on the total solid content of the image forming material,
It can be added to the image-forming material in a proportion of 0.01 to 10% by weight, preferably 0.1 to 3% by weight.

If necessary, a plasticizer is added to the image-forming material of the present invention in order to impart flexibility to the coating film. For example, butylphthalyl, polyethylene glycol, tributyl citrate, diethyl phthalate, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate,
Tricresyl phosphate, tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, acrylic acid or methacrylic acid oligomers and polymers, and the like are used.

[Lithographic printing plate precursor] The image forming material of the present invention can be preferably used as a recording layer of a lithographic printing plate precursor. Such a lithographic printing plate precursor is a lithographic printing plate prepared by dissolving a recording layer coating solution containing the image forming material of the present invention or a coating layer component of a desired layer such as a protective layer in a solvent and coating the solution on a suitable support. A printing plate precursor can be manufactured. As the solvent used here, ethylene dichloride, cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-methoxyethyl acetate, 1-methoxy-2-propyl acetate, dimethoxy. Examples include ethane, methyl lactate, ethyl lactate, N, N-dimethylacetamide, N, N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene and water. It is not limited to this. These solvents may be used alone or as a mixture. The concentration of the above components (total solids including additives) in the solvent is preferably 1 to 50% by weight. The coating amount (solid content) on the support obtained after coating and drying varies depending on the use, but is generally preferably 0.5 to 5.0 g / m ² for the photosensitive printing plate.
As the coating amount decreases, the apparent sensitivity increases, but the film characteristics of the recording layer deteriorate. As a method of coating, various methods can be used, for example, bar coater coating, spin coating, spray coating, curtain coating, dip coating, air knife coating, blade coating,
Examples thereof include roll coating.

In the coating solution for the recording layer using the image-forming material of the present invention, a surfactant for improving the coating property, such as a fluorine-based agent as described in JP-A-62-170950. Surfactants can be added. The preferable addition amount is 0.01 to 1% by weight, and more preferably 0.05 to 0.5% by weight, based on the whole image forming material.

As the support used for the lithographic printing plate precursor, a dimensionally stable plate-like material is used, and examples thereof include paper and plastic (eg, polyethylene, polypropylene,
Polystyrene laminated paper, metal plate (eg, aluminum, zinc, copper, etc.), plastic film (eg, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate butyrate, cellulose nitrate, polyethylene) Terephthalate, polyethylene, polystyrene, polypropylene, polycarbonate, polyvinyl acetal, etc.), paper laminated with the above metal, or vapor deposited, or a plastic film.

As the support used for the lithographic printing plate precursor, a polyester film or an aluminum plate is preferable, and among them, an aluminum plate which has good dimensional stability and is relatively inexpensive is particularly preferable. Suitable aluminum plate is a pure aluminum plate and aluminum as a main component,
It may be an alloy plate containing a trace amount of a foreign element, and may be a plastic film on which aluminum is laminated or vapor-deposited. The foreign elements contained in the aluminum alloy include silicon, iron, manganese, copper, magnesium, chromium, zinc,
Examples include bismuth, nickel, and titanium. The content of foreign elements in the alloy is at most 10% by weight. Aluminum which is particularly preferred in the present invention is pure aluminum, but completely pure aluminum is difficult to produce in terms of refining technology, and thus may contain a slightly different element. As described above, the composition of the aluminum plate applied to the present invention is not specified, and conventionally known and publicly known aluminum plates can be appropriately used. The thickness of the aluminum plate used in the present invention is about 0.1 m.
m to about 0.6 mm, preferably 0.15 mm to 0.4
mm, particularly preferably 0.2 mm to 0.3 mm.

Prior to the surface roughening of the aluminum plate, if desired, a degreasing treatment for removing the rolling oil on the surface is carried out with, for example, a surfactant, an organic solvent or an alkaline aqueous solution. Roughening treatment of the surface of the aluminum plate,
Various methods are used, for example, a method of mechanically roughening the surface, a method of electrochemically dissolving and roughening the surface, and a method of chemically selectively dissolving the surface. As the mechanical method, known methods such as a ball polishing method, a brush polishing method, a blast polishing method and a buff polishing method can be used. Further, as an electrochemical graining method, there is a method of performing alternating current or direct current in a hydrochloric acid or nitric acid electrolytic solution.
Further, as disclosed in Japanese Patent Laid-Open No. 54-63902, a method in which both are combined can be used.

The aluminum plate thus roughened is
If necessary, an alkali etching treatment and a neutralization treatment are carried out, and thereafter, if desired, an anodizing treatment is carried out in order to enhance water retention and abrasion resistance of the surface. As the electrolyte used for the anodizing treatment of the aluminum plate, it is possible to use various electrolytes which form a porous oxide film, generally sulfuric acid,
Phosphoric acid, oxalic acid, chromic acid or a mixed acid thereof is used. The concentration of these electrolytes is appropriately determined depending on the type of electrolyte.

The treatment conditions for anodization vary depending on the electrolyte used and cannot be specified unconditionally, but generally the concentration of the electrolyte is 1 to 80% by weight solution, the liquid temperature is 5 to 70 ° C., and the current density is 5 to 60 A. / Dm ² , voltage 1 to 100 V, electrolysis time 10 seconds to 5 minutes are suitable. If the amount of the anodic oxide film is less than 1.0 g / m ² , printing durability may be insufficient, or the non-image area of the planographic printing plate may be easily scratched.
So-called "scratch stains" tend to occur in which ink adheres to the scratched portion during printing.

After the anodizing treatment, the aluminum surface is optionally hydrophilized. Examples of the hydrophilic treatment used in the present invention include US Pat. No. 2,714,0
No. 66, No. 3,181,461, No. 3,280,7
No. 34 and 3,902,734, there are alkali metal silicate (eg sodium silicate aqueous solution) methods. In this method, the support is immersed in an aqueous sodium silicate solution or electrolyzed. In addition, potassium fluorozirconate disclosed in JP-B-36-22063 and US Pat. No. 3,2
No. 76,868, No. 4,153,461, No. 4,
The method of treating with polyvinylphosphonic acid as disclosed in No. 689,272 is used.

In the planographic printing plate precursor provided with a recording layer containing the image forming material of the invention, an undercoat layer may be provided between the support and the recording layer, if necessary. As the undercoat layer component, various organic compounds are used, for example, carboxymethyl cellulose, dextrin, gum arabic, 2
-Phosphonic acids having an amino group such as aminoethylphosphonic acid, phenylphosphonic acid which may have a substituent,
Organic phosphonic acids such as naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid, methylenediphosphonic acid and ethylenediphosphonic acid, phenylphosphoric acid which may have a substituent, naphthylphosphoric acid, alkylphosphoric acid and glycerophosphoric acid Organic phosphoric acid, phenylphosphinic acid which may have a substituent, naphthylphosphinic acid, organic phosphinic acid such as alkylphosphinic acid and glycerophosphinic acid, amino acids such as glycine and β-alanine,
And a hydrochloride of an amine having a hydroxy group such as a triethanolamine hydrochloride, etc., but two or more kinds may be mixed and used.

The lithographic printing plate precursor prepared as described above is usually subjected to image exposure and development. As a light source of actinic rays used for image exposure, wavelengths of 720 to 120
Solid-state lasers, semiconductor lasers, and the like that emit infrared rays of 0 nm are included. In the present invention, a light source having an emission wavelength in the near infrared to infrared region is preferable, and a solid laser and a semiconductor laser are particularly preferable.

As the developer and replenisher for the planographic printing plate precursor provided with the recording layer containing the image-forming material of the present invention, conventionally known alkaline aqueous solutions can be used. For example,
Sodium silicate, potassium silicate, sodium phosphate tribasic, potassium phosphate tribasic, ammonium phosphate tribasic,
Dibasic sodium phosphate, dibasic potassium phosphate, dibasic ammonium phosphate, sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonium hydrogen carbonate, sodium borate, potassium borate, ammonium borate, hydroxide Inorganic alkali salts such as sodium, ammonium hydroxide, potassium hydroxide and lithium hydroxide can be mentioned. Further, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monoisopropylamine, diisopropylamine, triisopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine,
Organic alkaline agents such as ethyleneimine, ethylenediamine and pyridine are also used.

These alkaline agents may be used alone or in combination of two or more. Among these alkaline agents, a particularly preferable developer is an aqueous silicate solution such as sodium silicate or potassium silicate. The reason is that silicon oxide SiO ₂ which is a component of silicate and alkali metal oxide
This is because the developing property can be adjusted by the ratio and concentration of M ₂ O. For example, JP-A-54-62004,
An alkali metal silicate as described in JP-B-57-7427 is effectively used.

Further, in the case of developing using an automatic processor, an aqueous solution (replenisher) having a higher alkaline strength than the developing solution.
It is known that a large amount of PS plate can be processed by replacing the developing solution in the developing tank for a long period of time without adding the developing solution to the developing solution. Also in the present invention, this replenishment system is preferably applied. Various surfactants and organic solvents can be added to the developing solution and the replenishing solution, if necessary, for the purpose of accelerating or suppressing the developing property, dispersing the development residue and improving the ink affinity of the printing plate image area. Preferred surfactants include anionic, cationic, nonionic and amphoteric surfactants. Further, in the developing solution and the replenishing solution, if necessary, a reducing agent such as a sodium salt or potassium salt of an inorganic acid such as hydroquinone, resorcin, sulfurous acid, and bisulfite, an organic carboxylic acid, a defoaming agent, and a water softener. It can also be added. The printing plate developed using the above-mentioned developing solution and replenishing solution is post-treated with washing water, a rinse solution containing a surfactant and the like, and a desensitizing solution containing gum arabic and a starch derivative. As the post-treatment when the image forming material of the present invention is used as a printing plate, various combinations of these treatments can be used.

In recent years, in the plate making / printing industry, automatic developing machines for printing plates have been widely used in order to rationalize and standardize the plate making work. This automatic developing machine is generally composed of a developing section and a post-processing section, and is composed of a device for conveying a printing plate, each processing liquid tank and a spraying device, which conveys an exposed printing plate horizontally while pumping it up with each pump. The processing liquid is sprayed from a spray nozzle for development processing. Further, recently, a method has also been known in which a printing plate is dipped and conveyed by a submerged guide roll or the like in a processing liquid tank filled with the processing liquid for processing. In such automatic processing, it is possible to perform processing while supplementing each processing solution with a replenishing solution according to the processing amount, operating time, and the like. Further, a so-called disposable processing method of processing with a substantially unused processing liquid can be applied.

The photosensitive lithographic printing plate precursor using the image forming material of the present invention will be described. Unnecessary if there are unnecessary image areas (for example, film edge traces of the original film) on the lithographic printing plate obtained by imagewise exposure, development, washing with water and / or rinsing and / or gumming. The image area is erased. Such erasing is preferably performed, for example, by applying an erasing liquid as described in Japanese Patent Publication No. 2-13293 to the unnecessary image portion, leaving it for a predetermined time as it is, and then rinsing with water. A method described in JP-A-59-174842, in which an active ray guided by an optical fiber is applied to an unnecessary image portion and then developed, can also be used.

The lithographic printing plate obtained as described above can be subjected to a printing step after applying a desensitizing gum if desired, but when a lithographic printing plate having higher printing durability is desired, Is subjected to a burning process. When the planographic printing plate is subjected to a burning treatment, before the burning treatment, Japanese Patent Publication Nos. 61-2518, 55-28062,
It is preferable to treat with a surface-adjusting solution as described in JP-A Nos. 62-31859 and 61-159655. As the method, with a sponge or absorbent cotton soaked with the surface-adjusting solution, it is applied on the lithographic printing plate, or by immersing the printing plate in a vat filled with the surface-adjusting solution, Application by an automatic coater is applied. Further, making the coating amount uniform with a squeegee or a squeegee roller after coating gives more preferable results.

The coating amount of the surface conditioning solution is generally 0.03 to 0.8.
g / m ² (dry weight) is suitable. The planographic printing plate coated with the surface-adjusting solution is dried if necessary, and then a burning processor (for example, a burning processor sold by Fuji Photo Film Co., Ltd .: “BP-130”).
0 ") and so on. The heating temperature and time in this case depend on the types of components forming the image,
The range of 180 to 300 ° C. and the range of 1 to 20 minutes are preferable.

The lithographic printing plate which has been subjected to the burning treatment can be subjected to conventional treatments such as washing with water and gumming, if necessary. When a liquid is used, so-called desensitizing treatment such as gumming can be omitted. The planographic printing plate obtained by such treatment is applied to an offset printing machine or the like and used for printing a large number of sheets.

[0190]

The present invention will be described below with reference to the following examples, but the scope of the present invention is not limited to these examples.

(Synthesis Example 1, Synthesis of IR-1) 2, 2 ',
2,4'-Tetrahydroxybenzophenone 24.6g
Was dissolved in 200 ml of methanol, 5.4 g of sodium methoxide was added, and the mixture was stirred at room temperature for 20 minutes. After stirring, the solvent was distilled off under reduced pressure to dissociate a part (about 25%) of the phenolic hydroxyl group to obtain a phenoxide. Furthermore, N,
It was dissolved in 200 ml of N-dimethylformaldehyde, 75.5 g of the following cyanine dye A was added, and the mixture was stirred at 50 ° C. for 4 hours. After stirring, the reaction solution was poured into 3000 ml of water, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 92.1 g of a mixture (IR-1) of a phenol oligomer modified with an organic group having infrared absorption ability. Obtained.

[0192]

[Chemical 27]

With respect to the obtained IR-1, ¹ H-NMR,
The structure of the main product was estimated by ¹³ C-NMR, IR spectrum and high performance liquid chromatography (HPLC). Further, the content rate of the main product was calculated from the peak area ratio of HPLC and found to be 72%. The structures of the main products are shown below.

[0194]

[Chemical 28]

The λ _{max of} IR-1 obtained was 801.
nm, absorbance per 1 g / l (in methanol) is 12
It was 8. The absorbance described here is the optical path length 1c.
It is the value obtained by dividing the absorbance measured in the cell of m by the concentration (g / l).

(Synthesis Example 2, Synthesis of IR-6) 1- [α-
Methyl-α- (4'-hydroxyphenyl) ethyl]-
4- [α, α'-bis (4 ''-hydroxyphenyl)
21.2 g of ethyl] benzene was dissolved in 150 ml of methanol, 2.7 g of sodium methoxide was further added, and the mixture was stirred at room temperature for 20 minutes. After stirring, the solvent was distilled off under reduced pressure to dissociate a part (about 33%) of the phenolic hydroxyl group to obtain a phenoxide. Furthermore, the above cyanine dye A37.8 was dissolved in 150 ml of N, N-dimethylformaldehyde.
g was added and the mixture was stirred at 50 ° C. for 4 hours. After stirring, the reaction solution was poured into 2000 ml of water, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain a mixture of phenol oligomers modified with an organic group having infrared absorption ability (IR-
6) 55.6 g was obtained.

With respect to the obtained IR-6, ¹ H-NMR,
The structure of the main product was estimated by ¹³ C-NMR, IR spectrum and high performance liquid chromatography (HPLC). Further, the content rate of the main product was calculated from the peak area ratio of HPLC and found to be 65%. The structures of the main products are shown below.

[0198]

[Chemical 29]

The λ _max of the obtained IR-6 was 801.
nm, absorbance per 1 g / l (in methanol) is 10
It was 8.

(Synthesis Example 3, Synthesis of IR-7) α, α,
α ′, α ′, α ″, α ″ -hexakis (4-hydroxyphenyl) -1,3,5-triethylbenzene 3
5.7 g was dissolved in 300 ml of methanol, 2.7 g of sodium methoxide was further added, and the mixture was stirred at room temperature for 20 minutes. After stirring, the solvent was distilled off under reduced pressure, and a part (about 17%) of the phenolic hydroxyl group was dissociated to obtain a phenoxide. Furthermore, it was dissolved in 250 ml of N, N-dimethylformaldehyde, 37.8 g of the above cyanine dye A was added, and the mixture was stirred at 50 ° C. for 6 hours. After stirring, the reaction solution was poured into 3000 ml of water, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to give 70.5 g of a mixture of phenol oligomers modified with an organic group having infrared absorption ability (IR-7). Obtained.

With respect to the obtained IR-7, ¹ H-NMR,
The structure of the main product was estimated by ¹³ C-NMR, IR spectrum and high performance liquid chromatography (HPLC). The content of the main product was found to be 52% from the peak area ratio of HPLC. The structures of the main products are shown below.

[0202]

[Chemical 30]

The λ _max of the obtained IR-7 is 801.
nm, absorbance per 1 g / l (in methanol) is 87
Met.

(Synthesis Example 4, Synthesis of IR-10)
The following phenol oligomer A31.4 g synthesized by the method described in Synthesis Example 14 of US Pat.
It was dissolved in 300 ml of N-dimethylformaldehyde, further added 8.6 g of 60% sodium hydride under a nitrogen atmosphere, and stirred at 50 ° C. for 60 minutes. Further, 37.8 g of the above cyanine dye A was added, and the mixture was heated to 50 ° C. and stirred for 6 hours. After stirring, the reaction solution was poured into 3000 ml of diluted hydrochloric acid, the precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 65.2 g of a mixture (IR-10) of a phenol oligomer modified with an organic group having infrared absorption ability. Obtained.

[0205]

[Chemical 31]

With respect to the obtained IR-10, ¹ H-NM
The structure of the main product was estimated by R, ¹³ C-NMR, IR spectrum and high performance liquid chromatography (HPLC). Further, the content ratio of the main product was determined from the peak area ratio of HPLC, and it was 58%. The structures of the main products are shown below.

[0207]

[Chemical 32]

The λ _max of the IR-10 obtained was 80.
Absorbance per 1 nm / g / l (in methanol) is 9
It was 2.

(Synthesis Example 5, Comparative Synthesis Example Using High Molecular Phenol NVK) 47.2 g of cresol-formaldehyde resin (m-cresol: p-cresol molar ratio 6: 4, weight average molecular weight 8,500) was added to N, It was dissolved in 400 g of N-dimethylformaldehyde, and 0.4 g of 60% sodium hydride was further added under a nitrogen atmosphere, and the mixture was allowed to stand at room temperature for 60%.
Stir for minutes. Furthermore, 15.1 g of the above cyanine dye A was added, and the mixture was heated to 60 ° C. and stirred for 6 hours. After stirring, the reaction solution was poured into 3500 ml of dilute hydrochloric acid, the precipitate was collected by filtration, washed with water, and dried under reduced pressure, whereby NVK resin (IR-E) 60. modified with an organic group having infrared absorption ability.
1 g was obtained. Λ _max of the obtained IR-E is 802 nm,
The absorbance per 1 g / l (in methanol) was 53.9.

[Production of Substrate] An aluminum plate (material 1050) having a thickness of 0.3 mm was washed with trichlorethylene to degrease it, and then the surface was grained using a nylon brush and 400 mesh pumice-water suspension. Washed well with water. The plate was etched by immersing it in a 25% aqueous sodium hydroxide solution at 45 ° C for 9 seconds, washed with water, and then further washed with water.
It was immersed in 0% nitric acid for 20 seconds and washed with water. At this time, the etching amount of the grained surface was about 3 g / m ² . Next, this plate was subjected to a current density of 15 A / dm ² using 7% sulfuric acid as an electrolytic solution.
After applying a DC anodic oxide coating of 3 g / m ² with water, wash with water,
Dry and further add 3% with a 2.5% by weight aqueous solution of sodium silicate.
Treat at 0 ° C for 10 seconds, apply the undercoating liquid below, and apply the coating to 8
A substrate was obtained by drying at 0 ° C for 15 seconds. The coating amount of the coating film after drying was 15 mg / m ² . [Undercoating liquid] -The following compound 0.3 g-Methanol 100 g-Water 1 g

[0211]

[Chemical 33]

Example 1 The following photosensitive solution 1 was applied to the obtained substrate so that the coating amount was 1.0 g / m ² (after drying), and then PERFECT OVEN manufactured by TABAI was used.
Wind Control was set to 7 in PH200 and dried at 140 ° C. for 50 seconds to obtain a lithographic printing plate precursor 1. [Photosensitive solution 1] m, p-cresol novolak 0.422 g (m / p ratio = 6/4, weight average molecular weight 3500, containing 0.5% by weight of unreacted cresol) -Specification described in JP-A-11-288093 Copolymer 1 2.37 g-Phenol oligomer of Synthesis Example 4 (IR-10) 0.207 g-2-Methoxy-4- (N-phenylamino) benzene diazonium-hexafluorophosphate 0.03 g-Tetrahydrophthalic anhydride 0 .19g-Ethyl violet counter ion converted to 6-hydroxy-β-naphthalenesulfonic acid 0.05g-Fluorine-based surfactant (Megafuck F176PF, manufactured by Dainippon Ink and Chemicals, Inc.) 0.035g-Fluorine -Based surfactant (Megafuck MCF-312, manufactured by Dainippon Ink and Chemicals, Inc.) 0.0 g · p-toluenesulfonic acid 0.008 g · bis -p- hydroxyphenyl sulfone 0.063 g · stearate n- dodecyl 0.06 g · .gamma.-butyrolactone 13 g · Methyl ethyl ketone 24 g · 1-Methoxy-2-propanol 11g

Example 2 The following photosensitive solution 2 was coated on the obtained substrate so that the coating amount was 1.6 g / m ² , and
The planographic printing plate precursor 2 was obtained by drying under the same conditions as in Example 1. [Photosensitive solution 2] 2.17 g of m, p-cresol novolak (m / p ratio = 6/4, weight average molecular weight 8500, containing 0.5% by weight of unreacted cresol) Octylphenol novolac (weight average molecular weight: 2500) 0.015 g-Phenol oligomer of Synthesis Example 1 (IR-7) 0.190 g-2-Methoxy-4- (N-phenylamino) benzene diazonium-hexafluorophosphate 0.03 g-Tetrahydrophthalic anhydride 0.10 g-Ethyl Violet counter ion is 6-hydroxy-β-naphthalene sulfonic acid 0.063g-Fluorosurfactant (Megafuck F176PF, Dainippon Ink and Chemicals, Inc.) 0.035g-Fluorosurfactant (Megafuck MCF-312, Dainippon Ink and Chemicals, Inc.) ) 0.13 g · bis -p- hydroxyphenyl sulfone 0.08 g · Methyl ethyl ketone 16g · 1-Methoxy-2-propanol 10g

[Examples 3 to 6] In the photosensitive solution 1 of Example 1, the alkali-soluble resin shown in Table 1 below was used in place of the m, p-cresol novolac and the phenol oligomer (IR-10) of Synthesis Example 4. Example 1 except that
Lithographic printing plate precursors 3 to 6 were obtained in the same manner as in.

[0215]

[Table 1]

[Comparative Example 1] In the photosensitive solution 1 of Example 1, the amount of m, p-cresol novolac was 0.474 g.
Except that 0.155 g of the above cyanine dye A was used instead of the phenol oligomer (IR-10), and a lithographic printing plate precursor 7 was obtained in the same manner as in Example 1.

[Comparative Example 2] In the photosensitive solution 2 of Example 2, 2.36 g of the novolak resin of Synthesis Example 5 was used instead of m, p-cresol novolac and the phenol oligomer.
In the same manner as in Example 2 except that the above was used, the planographic printing plate precursor 8
Got

[Example 7 and Comparative Example 3] The substrate used in Example 1 was coated with the following photosensitive solution A and dried at 100 ° C for 2 minutes to form a layer (A). The applied amount after drying is 0.8g
/ M ² . Then, the following photosensitive solutions B-1 and B-2 were applied and dried at 100 ° C. for 2 minutes to form a layer (B) (upper layer) to obtain planographic printing plate precursors 9 and 10. The total coating amount of the photosensitive liquid after drying was 1.8 g / m ² . [Photosensitive solution A] -Copolymer 1 0.75 g-Phthalocyanine dye B 0.04 g-p-toluenesulfonic acid 0.002 g-tetrahydrophthalic anhydride 0.05 g-Victoria Pure Blue BOH counter anion 1-naphthalene sulfone Dye 0.015 g converted to acid anion-Fluorosurfactant (Megafuck F-177, manufactured by Dainippon Ink and Chemicals, Inc.) 0.02 g-γ-butyrolactone 8 g-Methyl ethyl ketone 7 g-1-Methoxy-2-propanol 7 g

[0219]

[Chemical 34]

[0220] [Photosensitive liquid B-1, 2] ・ Novolak resin (listed in Table 2) -Phenol oligomer (IR-7) or cyanine dye A (listed in Table 2) -Stearate n-dodecyl 0.02g -Fluorine-based surfactant (MegaFac F-177,     Dainippon Ink and Chemicals Co., Ltd.) 0.05g ・ Methyl ethyl ketone 7g ・ 1-Methoxy-2-propanol 7 g

[0221]

[Table 2]

Example 8 The following photosensitive solution C was applied to the substrate used in Example 1 and dried at 100 ° C. for 2 minutes,
The (C) layer was formed. The applied amount after drying is 1.0 g / m ^2.
Met. After that, the above-mentioned photosensitive solution B-2 was applied, and 10
It was dried at 0 ° C. for 2 minutes to form a layer (B) (upper layer) to obtain a lithographic printing plate precursor 11. The total coating amount of the photosensitive liquid after drying was 1.6 g / m ² . [Photosensitive solution C] -Copolymer 1 0.75 g-Phenol oligomer of Synthesis Example 2 0.04 g-p-Toluenesulfonic acid 0.002 g-Tetrahydrophthalic anhydride 0.05 g-Victoria Pure Blue BOH counter anion 1 -Naphthalene sulfonate anion dye 0.015 g-Fluorosurfactant (Megafuck F-177, Dainippon Ink and Chemicals, Inc.) 0.02 g-γ-butyrolactone 8 g-Methyl ethyl ketone 7 g-1-methoxy- 2-propanol 7g

[Evaluation of lithographic printing plate precursor] [Scratch resistance test] Obtained lithographic printing plate precursor 1 of the invention
~ 6, 9 and 11 and lithographic printing plate precursors 7 and 8 of Comparative Examples
10 and the rotary ablation tester (T
(Manufactured by OYOSEIKI Co., Ltd.) was rubbed 30 times with Abraser Felt CS5 under a load of 250 g. afterwards,
Fuji Photo Film Co., Ltd. charged with Fuji Photo Film Co., Ltd. developer DT-1 (diluted 1: 8) and Fuji Photo Film Co., Ltd. finisher FP2W (diluted 1: 1). Development was performed using a PS processor 900H at a liquid temperature of 30 degrees and a development time of 12 seconds. The electric conductivity of the developing solution at this time was 45 mS / cm.

The scratch resistance was evaluated according to the following criteria. Party A: The optical density of the photosensitive film in the rubbed part did not change at all. B: The optical density of the photosensitive film in the rubbed part was slightly observed visually. 丙: The optical density of the photosensitive film in the rubbed part was 2 / of non-rubbing part
Table 3 shows the results of the scratch resistance evaluation for those with a score of 3 or less.

[0225]

[Table 3]

As is apparent from Table 3, the lithographic printing plate precursor using the image forming material of the present invention as the recording layer was found to have excellent scratch resistance.

[Evaluation of Image Formability] The lithographic printing plate precursors 1 to 6, 9 and 11 of the present invention thus obtained and the lithographic printing plate precursors 7, 8 and 10 of Comparative Examples were prepared by Trendo manufactured by Creo.
Beam intensity 9 t, drum rotation speed 150r at tter
An image of the test pattern was drawn with pm. First, the lithographic printing plate precursors 1 to 11 exposed under the above conditions,
Fuji Photo Film Co., Ltd. developer DT-1 (1: 9.5
And a finisher FP2W (produced by Fuji Photo Film Co., Ltd.) diluted with Fuji Photo Film Co., Ltd. (PS) 900H manufactured by Fuji Photo Film Co., Ltd. It was developed in 12 seconds. The electric conductivity of the developer at this time is 40 mS / cm, respectively.
Met.

The presence or absence of ablation during exposure was visually confirmed. In addition, the exposed area (non-image area) after development was visually observed for stains or coloration due to the residual film of the recording layer that had poor development. The results are shown in Table 4.

[0229]

[Table 4]

As is clear from Table 4, in the lithographic printing plate precursor using the image forming material of the present invention in the recording layer, a high quality image without stain is formed in the non-image area after development, and ablation occurs. It was found that the image forming property was excellent. From each of the above examples, the image-forming material containing the infrared absorbing oligomer of the present invention can be recorded with high sensitivity by an infrared laser, has excellent scratch resistance, and a high-quality image with no stain on the non-image area can be obtained. It was found that the formation of ablation can also be suppressed.
That is, the infrared absorbing oligomer of the present invention was useful as an image forming material.

[0231]

INDUSTRIAL APPLICABILITY The image forming material of the present invention is excellent in image forming property and storage stability, and has an effect that an image can be formed by an infrared laser for direct plate making without contaminating an optical system of an exposure device. . Further, the novel oligomer having an infrared absorbing ability of the present invention, which can be suitably used for this image forming material, is useful as an image forming material.

Continued front page    F term (reference) 2H025 AA04 AA11 AB03 AC01 AC08                       AD01 AD03 BC13 BC42 BE00                       BE10 BG00 CA00 CB08 CB14                       CB20 CB23 CB28 CB42 CC13                       CC20 FA17                 2H096 AA06 BA01 BA11 EA04 EA23                       GA08                 4C204 BB05 BB09 CB13 DB15 EB10                       FB03 GB01

Claims (3)

[Claims] 1. An image-forming material comprising at least one hydroxyl group containing a phenol oligomer modified with an organic group having an infrared absorption ability, and capable of recording by infrared exposure. 2. An alkaline aqueous solution containing (a) a phenolic oligomer having at least one hydroxyl group modified with an organic group having an infrared absorbing ability, and (b) a polymer compound soluble in an alkaline aqueous solution, which are exposed to infrared rays. An image-forming material characterized in that its solubility in water is changed. 3. A phenol oligomer in which at least one hydroxyl group is modified with an organic group capable of absorbing infrared rays.